JP7348162B2 - Additive manufacturing methods using materials with soft tissue properties - Google Patents

Description

RELATED APPLICATIONS This application is filed under U.S. Provisional Patent Application No. U.S. Provisional Patent Application No. 62/538006, 62/538015, 62/538018, and 62/538026 filed on July 28, 2017. 62/538003.

The contents of the above applications are hereby incorporated by reference in their entirety as if fully set forth herein.

TECHNICAL FIELD The present invention, in some embodiments, relates to additive manufacturing (AM), in particular but not limited to additive manufacturing, from soft materials having, at least in part, the properties of soft body tissue (e.g., mechanical and/or visual properties). Concerning the additive manufacturing of manufactured objects.

Additive manufacturing is generally a method in which three-dimensional (3D) objects are manufactured using a computer model of the object. Such methods are used in various fields such as design-related fields for visualization, demonstration and mechanical prototyping, and rapid manufacturing (RM) purposes.

The basic operation of any AM system consists of slicing the three-dimensional computer model into thin cross-sections, converting the results into two-dimensional position data, and feeding the data to a controller that fabricates the three-dimensional structure layer by layer.

Various AM technologies exist, among them stereolithography, digital light processing (DLP), and three-dimensional (3D) printing (particularly 3D inkjet printing). Such techniques are typically carried out by layer-by-layer deposition and solidification of one or more construction materials, typically photopolymerizable (photocurable) materials.

In a three-dimensional printing process, for example, a build material is ejected from a dispensing head having a set of nozzles to deposit a layer on a support structure. Depending on the construction material, the layer can then be cured or solidified using suitable equipment.

Various three-dimensional printing techniques exist, such as U.S. Patent Nos. 6,259,962; 6,569,373; No. 335, No. 7,209,797, No. 7,225,045, No. 7,300,619, No. 7,479,510, No. 7,500,846, No. 7,962,237 and No. 9,031,680. They all have the same applicant, the contents of which are incorporated herein by reference.

Printing systems used in additive manufacturing can include a receiving medium and one or more printheads. The receiving medium can be, for example, a fabrication tray that can include a horizontal surface for carrying material ejected from the print head. The printhead can be, for example, an inkjet head having a plurality of ejection nozzles arranged in one or more rows along the longitudinal axis of the printhead. The printhead can be positioned such that its longitudinal axis is substantially parallel to the pointing direction.

The printhead is connected to a controller, such as a microprocessor, that controls the printing process, including movement of the printhead according to a predefined scanning plan (CAD configuration converted to stereolithography (STL) format and programmed into the controller). may further include. The print head can include multiple jetting nozzles. The injection nozzle expels the material onto the receiving medium, creating a layer representing the cross-section of the 3D object.

In addition to the print head, a source of curing conditions may be present to cure the ejected build material. Curing conditions typically include curing energy, typically radiation, such as UV radiation.

In addition, the printing system can include a leveling device for leveling and/or establishing the height of each layer after deposition and before subsequent deposition of the layer after at least partial solidification.

Build materials can include building materials and support materials that form the object and the temporary support structure that supports the object as it is constructed.

The building material (which may include one or more materials in one or more formulations) is deposited to produce the desired object, and the support material (which may include one or more materials) is deposited to produce the desired object. can be used with or without building material elements to provide support structure for specific areas of an object during construction, e.g. when the object has protruding features such as curved geometries, negative angles, gaps, etc. ensure proper vertical alignment of successive layers of matter.

Both the build material and the support material are liquid at the operating temperature at which they are dispensed and are then typically cured upon exposure to curing conditions (e.g., UV curing) to form the desired layer shape. It is preferable to do so. After printing is complete, the support structure is removed to reveal the final shape of the fabricated 3D object.

Multiple additive manufacturing processes enable additive formation of objects using more than one type of building material. For example, the applicant's Publication No. U.S. Patent Application No. 2010/0191360 describes a solid freeform fabrication apparatus having a plurality of dispensing heads, a build material feeder configured to feed a plurality of build materials to the fabrication apparatus, and a control for the fabrication apparatus and the feeder. A system is disclosed that includes a control unit configured to. The system has multiple modes of operation. In one mode, all jet heads are activated during a single build scan cycle of the fabrication equipment. In another mode, one or more of the ejection heads are not activated during a single build scan cycle or a portion thereof.

In a 3D inkjet printing process, such as Polyjet (Stratasys Ltd., Israel), build materials are selectively jetted from one or more printheads and printed in predetermined shapes as defined by a software file. It is deposited on the fabrication tray in successive layers according to the configuration.

Assigned US Pat. No. 9,227,365 discloses a solid free form sheathed object consisting of a plurality of layers and a layered core forming a core region and a layered sheath forming a jacket region. A method and system for fabrication is disclosed.

Additive manufacturing processes have been used to form rubber-like materials. For example, rubber-like materials are used in the PolyJet™ system as described herein. These materials are formulated to have a relatively low viscosity to enable e.g. ink-jet delivery and to exhibit a T _g below room temperature, e.g. 10<0>C or below. The latter is obtained by formulating compounds with a relatively low degree of crosslinking and by using monomers and oligomers (eg acrylic elastomers) with inherent flexibility-limiting molecular structures.

An exemplary family of rubber-like materials (sold under the trade name "Tango" family) that can be used in PolyJet(TM) systems has been found to have properties that include Shore A hardness, elongation at break, tear resistance, and tensile strength. Provides various elastomeric properties of the cured material. The softest material of this family has a Shore A hardness of 27.

Another family of rubber-like materials (sold under the trade name "Agilus" family) that can be used in the PolyJet(TM) system is described in PCT International Application No. 1 by the Applicant. IL2017/050604 (published as WO2017/208238) and uses an elastomeric curable material and silica particles.

Until now, additive manufacturing techniques have been used to use building materials that, when cured, have the hardness and appearance of soft body tissue, and thus, at least in part, mechanical and optionally visual properties similar to body soft tissue. There are no reports of additive manufacturing techniques that can produce 3D objects containing hardened materials that do.

According to an aspect of some embodiments of the invention, there is provided a method of additively manufacturing an object having soft tissue properties, the method comprising sequentially manufacturing a plurality of layers in a pattern of construction corresponding to the shape of the object. dispensing at least one build material formulation to form a hardness of at least a portion of the layer, the dispensing, when cured, having a Shore A hardness of less than 10 or a Shore OO of less than 40. A method is provided of a building material formulation having hardness.

According to some of any of the embodiments described herein, the discharge is of at least two build material formulations, and at least one of the build material formulations is cured. the building material formulation having a Shore A hardness of less than 10 or a Shore OO hardness of less than 40, wherein at least one of the building material formulations comprises at least one elastomeric curable material; It is a sexual compound.

According to some of any of the embodiments of the invention, the elastomeric curable formulation further comprises silica particles. According to some embodiments of the invention, the elastomeric curable formulation is selected from the group consisting of the Tango, Tango+, and Agilus families described below. at least one formulation of the formulation family.

According to some of any of the embodiments of the present invention, the extrudate comprises the building material formulation having a Shore A hardness of less than 10 or a Shore OO hardness of less than 40 when cured; and forming a voxel element containing the composition.

According to some of any embodiments of the invention, the interlaced locations occupied by the elastomeric curable formulation constitute about 10% to about 30% of the area of the layer.

According to some of any embodiments of the invention, the interlaced locations occupied by the elastomeric curable formulation constitute about 15% to about 25% of the area of the layer.

According to some of any of the embodiments of the invention, voxel elements comprising the elastomeric curable formulation form a capacitive fiber pattern in the object.

According to some of any embodiments of the invention, the fiber thickness characteristic of the fiber pattern is between about 0.4 mm and about 0.6 mm.

According to some of any of the embodiments of the invention, said fiber pattern is perpendicular to at least two or three planes of said layer.

According to some of any of the embodiments of the invention, the fiber pattern is oblique to at least two or three planes of the layer.

According to some of any of the embodiments of the invention, the method further comprises reinforcing each of at least two or three of the layers using a roller, wherein the diagonal fiber pattern substantially parallel to the tear force applied by the roller on the layer.

According to some of any embodiments of the invention, the fiber pattern forms an angle with the plane of about 30° to about 60°.

According to some of any embodiments of the invention, the method further includes forming a sheath covering an object from the elastomeric curable formulation.

According to some of any of the embodiments of the invention, the thickness of the sheath, measured perpendicular to the outermost surface of the sheath, is from about 0.4 mm to about 1 mm.

According to part of any of the embodiments of the invention, the method includes forming a sheath covering an object from the elastomeric building compound, and removing the sheath after completion of the additive manufacturing of the three-dimensional object. It further includes:

According to some of any of the embodiments of the invention, the building material formulation having the Shore A hardness and the Shore OO hardness when cured comprises a curable material and a non-curable material. , the amount of said non-curable material ranges from 10 to 49% or from 10 to 30% by weight of the total weight of said formulation.

According to some of any of the embodiments of the invention, the amount of said non-curable polymeric material ranges from 20 to 40 or from 25 to 40% by weight of the total weight of the formulation.

According to some of any of the embodiments of the invention, the non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, such as from about 1000 to about 4000 or from about 1500 to about 4000 or about 2000 Daltons. to about 4000 or about 1500 to about 3500 or about 2000 to about 3500 Daltons), and a Tg of less than 0°C or less than -10°C or less than -20°C.

According to some of any embodiments of the invention, the non-curable polymeric material comprises polypropylene glycol.

According to some of any of the embodiments of the invention, the non-curable polymeric material is a block copolymer comprising at least one polypropylene glycol block.

According to some of any of the embodiments of the invention, the non-curable polymeric material is a block copolymer comprising at least one polypropylene glycol block and at least one polyethylene glycol block; The total amount of glycol is 10% by weight or less.

According to some of any of the embodiments of the invention, the ratio of polypropylene glycol blocks to polyethylene glycol blocks in the block copolymer is at least 2:1.

According to some of any of the embodiments described herein, the ratio of polypropylene glycol backbone units to polyethylene glycol backbone units in the block copolymer is at least 2:1.

According to some of any of the embodiments of the invention, the non-curable polymeric material comprises polypropylene glycol and/or a block copolymer comprising at least one polypropylene glycol block, each of the polypropylene glycol blocks comprising at least one polypropylene glycol block. It has a molecular weight of 2000 Daltons.

According to some of any of the embodiments of the invention, the ratio of the amount of curable material to the amount of non-curable polymeric material is between 4:1 and 1.1:1 or between 3:1 and 2: The range is 1.

According to some of any of the embodiments of the invention, the amount of said curable material ranges from 55 to 70% by weight.

According to some of any embodiments of the invention, the curable material includes at least one monofunctional curable material and at least one multifunctional curable material.

According to some of any of the embodiments of the invention, the amount of said monofunctional curable material ranges from 50 to 89% by weight of the total weight of said formulation.

According to some of any of the embodiments of the invention, the amount of said multifunctional curable material ranges from 1 to 10% by weight of the total weight of said formulation.

According to some of any of the embodiments of the invention, the formulation comprises a monofunctional curable material in an amount of about 50% to about 89% by weight of the total weight of the formulation, about 10% by weight of the total weight of the formulation. A non-curable polymeric material in an amount of from about 49% by weight and a multifunctional curable material in an amount from about 1 to about 10% by weight of the total weight of the formulation.

According to some of any of the embodiments of the invention, (i) said non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, and/or (ii) said non-curable and (iii) at least 80% by weight of the total amount of said monofunctional curable material and said multifunctional curable material. includes a curable material that, when cured, has a Tg of less than 0°C or less than -10°C or less than -20°C.

According to some of any of the embodiments of the invention, the amount of said monofunctional curable material ranges from 50 to 60% or from 55 to 60% by weight of the total weight of the formulation.

According to some of any of the embodiments of the invention, the amount of said multifunctional curable material ranges from 3 to 10% or from 5 to 10% by weight of the total weight of the formulation.

According to some of any of the embodiments of the invention, the monofunctional curable material has a Tg of less than -10°C or less than -20°C when cured.

According to some of any embodiments of the invention, the monofunctional curable material comprises a hydrophobic monofunctional curable material.

According to some of any of the embodiments of the invention, the monofunctional curable material comprises an amphiphilic monofunctional curable material.

According to some of any of the embodiments of the invention, the monofunctional curable material comprises an amphiphilic monofunctional curable material that includes a hydrophobic moiety.

According to some of any of the embodiments of the invention, the monofunctional curable material comprises an amphiphilic monofunctional curable material (e.g., comprising a hydrophobic group or moiety); and a hydrophobic monofunctional curable material. including.

According to some of any of the embodiments of the invention, the weight ratio of said amphiphilic monofunctional curable material (eg, comprising a hydrophobic group or moiety) to said hydrophobic monofunctional curable material is 1. It is in the range of 5:1 to 1.1:1.

According to some of any of the embodiments of the invention, the multifunctional curable material has a Tg of less than -10°C or less than -20°C when cured.

According to some of any of the embodiments of the invention, the multifunctional curable material is a bifunctional curable material.

According to some of any of the embodiments of the invention, the monofunctional curable material is a UV curable material.

According to some of any of the embodiments of the invention, the monofunctional curable material is a monofunctional acrylate.

According to some of any of the embodiments of the invention, the multifunctional curable material is a UV curable material.

According to some of any of the embodiments of the invention, the multifunctional curable material is a multifunctional acrylate.

According to some of any of the embodiments of the invention, the formulation further comprises a photoinitiator.

According to some of the embodiments of the invention, the amount of photoinitiator ranges from 1 to 3% by weight of the total weight of the formulation.

According to some of the embodiments of the invention, the formulation further comprises a cure inhibitor in an amount ranging from about 0.01 to about 0.5% by weight of the total weight of the formulation.

According to some of any of the embodiments of the invention, the formulation further comprises at least one additive selected from colorants (pigments), surfactants, impact modifiers, and the like.

According to some of any of the embodiments of the invention, the formulation further comprises a surfactant, such as a UV curable surfactant.

According to some of any of the embodiments of the invention, when cured, the curable formulation contains a monofunctional compound (including the hydrophobic moiety) in an amount of 25 to 35% by weight of the total weight of the formulation. amphiphilic acrylates, monofunctional hydrophobic acrylates in an amount of 25-30% by weight of the total weight of the formulation, polyfunctional acrylates in an amount of 5-10% by weight of the total weight of the formulation, and 30-35% by weight of a non-curable polymeric material having a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons and a Tg of less than 0°C or less than -10°C or less than -20°C.

According to some of any of the embodiments of the invention, the non-curable polymeric material comprises polypropylene glycol and/or a block copolymer comprising at least one polypropylene glycol block, each of the at least one polypropylene glycol block has a molecular weight of at least 2000 Daltons.

According to some of the embodiments of the invention, the polyfunctional acrylate is a urethane diacrylate.

According to some of any of the embodiments of the invention, the monofunctional amphiphilic acrylate comprises a hydrocarbon chain of at least 6 carbon atoms and at least 2 alkylene glycol groups.

According to some of any of the embodiments of the invention, the monofunctional hydrophobic acrylate comprises a hydrocarbon chain of at least 8 carbon atoms.

According to some of any of the embodiments of the invention, the formulation having the Shore hardness when cured is further characterized by a tear resistance of at least 100 N/m.

According to some of any of the embodiments of the invention, the formulation having the Shore hardness when cured is further characterized by a compressive modulus of at least 0.01 MPa.

According to some of any of the embodiments of the invention, at least the building material formulation having the Shore hardness when cured is devoid of biological material.

According to some of any of the embodiments of the invention, at least the building material formulation having the Shore A hardness, when cured, comprises less than 10% water by weight.

According to some of any of the embodiments of the invention, at least the building material formulation having the Shore hardness when cured further comprises a pigment that imparts a red color to the formulation when cured. include.

According to some of any of the embodiments of the invention, the elastomeric curable formulation further comprises a pigment that imparts a white opaque color with yellow to the formulation when cured.

According to some of the embodiments of the invention, the amount of said pigment ranges from 0.01 to 5% by weight of the total weight of the formulation.

According to an aspect of some embodiments of the invention, a three-dimensional object having at least the visual or mechanical properties of a soft body tissue or organ created by a method described herein, the object comprising: , in at least a portion thereof, a material having a Shore A hardness of less than 10 or a Shore OO hardness of less than 40 is provided.

According to an aspect of some embodiments of the invention, a three-dimensional object having at least the visual or mechanical properties of a soft body tissue or body organ or a system or structure including the same, the object comprising at least one of the following: In some, objects are provided that include a material with a Shore A hardness of less than 10 or a Shore OO hardness of less than 40 and are devoid of biological material.

According to some of the embodiments of the invention, the object has at least the shape and hardness of the soft body tissue or system, structure or organ containing it.

Unless defined otherwise, all technical and/or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, exemplary methods and/or materials are described below. In case of conflict, the patent specification, including definitions, will control. In addition, the materials, methods and examples are illustrative only and not intended to be limiting.

Executing the methods and/or systems of embodiments of the present invention includes performing or completing selected tasks manually, automatically, or a combination thereof. Furthermore, depending on the actual equipment and apparatus of the embodiments of the methods and/or systems of the present invention, a number of selected steps may be performed by hardware, software, or firmware, or a combination thereof using an operating system.

For example, hardware for performing selected tasks according to embodiments of the invention may be implemented as a chip or a circuit. As software, selected tasks according to embodiments of the present invention may be implemented as software, such as software instructions executed by a computer using a suitable operating system. In example embodiments of the invention, one or more tasks according to example embodiments of the methods and/or systems described herein are performed on a data processor, e.g., a computing platform that executes a plurality of instructions. be done. Optionally, the data processor includes volatile memory for storing instructions and/or data, and/or non-volatile storage for storing instructions and/or data (e.g., a magnetic hard disk and/or removable recording medium). Optionally, network connectivity is further provided. A display and/or user input device (eg, keyboard or mouse) is optionally further provided.

Some embodiments of the invention are described herein by way of example only and with reference to the accompanying drawings. With particular reference to the drawings, it is emphasized that the details shown are for the purpose of illustrating and discussing embodiments of the invention by way of example only. In this regard, the description given in conjunction with the drawings will make it clear to those skilled in the art how to implement embodiments of the invention.

FIG. 1A is a schematic diagram of an additive manufacturing system according to some embodiments of the invention. 1B-1C are schematic diagrams of additive manufacturing systems according to some embodiments of the invention. FIG. 1D is a schematic diagram of an additive manufacturing system according to some embodiments of the invention.

2A-2C are schematic illustrations of printheads according to some embodiments of the invention.

3A and 3B are schematic diagrams demonstrating coordinate transformation according to some embodiments of the invention.

FIG. 4 is a flowchart illustration of a suitable method for making articles by additive manufacturing in accordance with aspects of some embodiments of the invention.

FIG. 5 is a schematic illustration of a region containing interlaced building material.

6A-6D are schematic diagrams of representative non-limiting examples of structures according to aspects of some embodiments of the invention.

Figure 7 gives the Shore hardness values of Shore OO, A and D of the known article.

FIG. 8 shows elliptical objects (left and center objects) made from soft material formulations according to some embodiments of the present invention, and from elastomeric building formulations and soft material formulations according to some embodiments of the present invention. Provides an image of an elliptical object (right object) made from a scaffold of the fabricated composition, all covered by a thin sheath made from an elastomeric modeling compound.

9A-9B are a schematic diagram of a printing scheme for forming regions containing interlaced build material (FIG. 9A) and an image showing an exemplary laminate printed according to the scheme shown in FIG. 9A (FIG. 9A-9B). FIG. 9B), which provides an exemplary soft material according to some of the present embodiments having 19% scaffold made from an elastomeric building compound (eg, but not limited to Agilus, such as Agilus 30). Scaffold composition structure of material formulation (BM61) is provided.

9C-9D are made from an exemplary soft material formulation (BM19) according to some of the present embodiments reinforced with a scaffolding structure (19% 0.5 mm beam) made from an elastomeric building compound. A heart model (FIG. 9C) and a diagram of its interior (FIG. 9D) are provided.

FIG. 10 is an image of an object made from an exemplary soft material formulation (BM61) according to some of the present embodiments with a 19% scaffold and a 0.6 mm coverage made from an elastomeric building compound. , it resists suturing/sewing.

FIGS. 11A-11B illustrate an exemplary soft material formulation according to some of the present embodiments having a 19% scaffold and a 0.6 mm coverage made from an elastomeric build material formulation when implemented in a medical device. Provides an image of a heart-shaped object made from BM61).

FIG. 12 provides a Jarvik heart model used in experiments performed according to some embodiments of the invention.

FIGS. 13A-13B illustrate an exemplary soft coating according to some of the present embodiments with a 0.6 mm coverage and 19% scaffolding made from an elastomeric building compound printed in a mode where the rollers rotated at a speed of 600 RPM. Image of the cardiographic model made from the material formulation (BM61) with the defect area indicated by a dotted circle (FIG. 13A) and the cardiographic model printed in a mode in which the rollers rotated at a speed of 412 RPM. , whose outer surface is smoother (FIG. 13B).

Figure 14 shows a 0.6 mm coating made from an elastomeric building compound and printed in a mode in which a feature gap was used (object on the right) and in a mode in which a feature gap was not used (object on the left). Provides an image of a heart model made from an exemplary soft material formulation according to some of the present embodiments with a scaffold of 19%, with the area with defects marked by a dotted circle above the image of the heart model on the left. It is shown.

Figure 15 provides a schematic diagram showing the forces applied between the roller and the ejected layer.

16A-16F illustrate several experimental reinforcement patterns tested in experiments conducted in accordance with some embodiments of the invention.

FIG. 17 is an image of four heart models printed in experiments performed in accordance with some embodiments of the invention.

FIG. 18A is a flowchart diagram describing an example procedure that may be used according to some embodiments of the invention to obtain computer object data. FIG. 18B is a flowchart diagram describing an example procedure that may be used according to some embodiments of the invention to obtain computer object data.

In some embodiments, the present invention relates to additive manufacturing (AM), in which soft materials are made from soft materials that have, at least in part, the properties of soft body tissues (e.g., mechanical and/or visual properties). related to additive manufacturing of objects.

Before describing in detail at least one embodiment of the invention, the present invention, in its application, will be described with reference to the components and/or methods set forth in the following description and/or illustrated in the drawings and/or examples. It should be understood that the invention is not necessarily limited to the details of assembly and construction. The invention is capable of other embodiments or of being practiced or carried out in various ways.

Currently used additive manufacturing methods, particularly those that utilize multiple material methodologies (e.g. PolyJet®), are made from materials with a wide range of properties including, for example, hardness, strength, color, and transparency. It allows the fabrication of objects that can be combined in the same object in any spatial distribution at the sub-millimeter scale. Such methods can be used to reproduce highly heterogeneous objects with different visual, mechanical, and/or even functional properties on a sub-millimeter scale according to a predetermined distribution. can.

The inventors sought to exploit additive manufacturing methods, particularly using multi-material techniques, to create objects that mimic the organs and tissues of the body. The organs of the body have a highly heterogeneous structure, which also varies from person to person. Such objects can be utilized as non-cellularized artificial biomimetics for a variety of uses, such as medical training systems, pre-surgical models, phantom images, implants, and educational examples.

To date, there have been additive manufacturing (e.g., 3D inkjet printing) methodologies for producing objects with structures and optionally partial appearances that resemble certain body parts; and tissue, especially soft body tissue, and the body organs that contain it cannot be manufactured with similar mechanical properties.

As mentioned above, the lowest Shore hardness value ever obtained for a cured material obtained by additive manufacturing methods is about 30 on the Shore A scale. Such hardness is substantially higher than that of soft tissues of the body, and therefore currently used methodologies are unable to fabricate objects that mimic soft tissues and the organs that contain them.

The Shore hardness of currently practiced 3D inkjet printed curable materials is primarily due to the exclusive inclusion of the curable material in the formulation that provides it.

Materials exhibiting low hardness, as indicated above, are generally gel-like materials (e.g. materials with the mechanical properties of a gel), which can be obtained from formulations containing non-curable materials in addition to curable materials. can get. Such gel-like materials are currently most often used in additive manufacturing as support materials, where the support materials are intended to be removed at the end of the process and do not form part of the final object.

As used herein and in the industry, the term "gel" refers to a material, often also referred to as a semi-solid material, which generally includes a three-dimensional solid network, which generally has a chemical relationship between them. It is made up of physically or physically interconnected fibrous structures and a liquid phase engaged within this network. Gels are generally characterized by a solid (e.g. non-fluid) consistency, a relatively low tensile strength, a relatively low shear modulus, e.g. less than 100 kPa, and a shear loss modulus to shear storage modulus (tan δ) of less than 1. , G′′/G).

The gel-like material according to this embodiment is a generally soft material, which can be a gel or a solid, and which has the mechanical and flow properties of a gel.

However, such gel-like materials exhibit low tensile strength and low tear resistance, and therefore break easily under stress, highly undesirable properties in additive manufacturing in general and in 3D inkjet printing in particular, and even when exposed to water. and susceptible to damage during use. Furthermore, gel-like materials generally present printing reliability problems such as smearing and sticking, and also have low dimensional stability due to leakage, leaching or drying. Gel-like materials are further limited by their ability to swell other components or to dry and change their morphology and dimensions in certain environmental conditions, thus making them incompatible when used in multi-material (e.g. digital materials) technology. or at least may form unstable objects.

Solutions to the limitations associated with utilizing formulations that provide gel-like materials when cured include the use of reinforcing materials that provide improved strength or materials that exhibit the desired stiffness and/or durability. Such a solution can impart overall properties, especially hardness, to the cured material that exceed the target properties.

Liquid materials can also be added to the formulation to balance the overall properties, but such materials may not adversely affect the performance of the resulting object, e.g., causing a "bleeding" effect. sell.

The inventors are interested in objects having the properties of body organs and tissues, in particular objects having at least in part properties similar to soft body tissues, such as the structure of body organs including soft tissues, visual, mechanical, and Additive manufacturing methods, such as 3D inkjet printing, have been designed and successfully implemented for the successful fabrication of objects that mimic functional properties.

These methods utilize curable formulations that, when cured, have Shore hardness values similar to those of soft tissue, and process parameters that allow additive manufacturing of soft materials to be carried out alone or in combination with other curable formulations. and technology. The designed method is designed to be similar to body soft tissues and/or organs containing it, while meeting process parameters such as suitability for the AM technology used (e.g. 3D inkjet printing), and in addition to the required hardness. It is possible to use formulations that give soft materials while providing objects with dimensional stability, sufficient tear resistance and visual properties.

The method and system of the present embodiments fabricate a three-dimensional object layer by layer based on computer object data by forming a plurality of layers with a configuration pattern that corresponds to the shape of the object. Computer object data can be formatted in Standard Tessellation Language (STL) or Stereolithography Contour (SLC) format, Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Exchange Format (DXF), Polygon File Format ( PLY), or any other format suitable for computer-aided design (CAD).

The term "object" as used herein refers to an entire article or a portion thereof.

Each layer is formed by additive manufacturing equipment that scans a two-dimensional surface and patterns it. During scanning, the device visits a plurality of target locations on the two-dimensional layer or surface and determines, for each target location or group of target locations, whether the target location or group of target locations is to be occupied by the build material formulation. Determine whether and what type of build material formulation should be delivered there. The determination is made according to a computer image of the surface.

In a preferred embodiment of the invention, AM comprises three-dimensional printing, more preferably three-dimensional inkjet printing. In these embodiments, the build material formulation is dispensed from a dispensing head having a set of nozzles to deposit the build material formulation in a layer onto the support structure. The AM device thus dispenses the build material formulation into the target locations to be occupied and leaves other target locations empty. The device typically includes a plurality of dispensing heads, each dispensing head can be configured to dispense a different build material formulation. Therefore, different target locations can be occupied by different build material formulations. Types of build material formulations can be divided into two main categories: building material formulations and support material formulations. The support material formulation serves as a support matrix or support structure to support the object or part of the object during the fabrication process and/or for other purposes, for example to provide a hollow or porous object. The support structure may further include building material formulation elements, for example to increase support strength. Support material formulations generally provide a gel or gel-like material when cured.

Build material formulations are generally compositions that are formulated for additive manufacturing and are capable of forming three-dimensional objects by themselves, that is, without the need to mix or combine with other substances. can.

The final three-dimensional object is made from the building material formulation, or a combination of the building material formulation and the support material formulation, or a modification thereof (eg, after curing). All of these operations are well known to those skilled in the art of solid freeform fabrication.

In some exemplary embodiments of the invention, objects are manufactured by dispensing two or more different build material formulations, each material formulation being dispensed from a different dispensing head of the AM. The material formulation is optionally and preferably deposited in layers during the same pass of the print head. The material formulations and combinations of material formulations within the layers are selected according to the desired properties of the object.

A representative, non-limiting example of a system 110 suitable for AM of an object 112 is shown in FIG. 1A, according to some embodiments of the invention. System 110 includes additive manufacturing equipment 114 having a dispensing unit 16 that includes a plurality of dispensing heads. Each head preferably includes an array of one or more nozzles 122 from which liquid build material formulation 124 is dispensed, as shown in FIGS. 2A-2C below.

Device 114 is preferably, but not necessarily, a three-dimensional printing device. In that case, the ejection head is a printing head and the build material formulation is ejected by inkjet technology. This is not necessarily the case, as in some applications additive manufacturing equipment may not need to employ three-dimensional printing techniques. Representative examples of additive manufacturing equipment contemplated in accordance with various exemplary embodiments of the present invention include, but are not limited to, fused additive manufacturing equipment and fused material formulation deposition equipment.

Each dispensing head is optionally and preferably fed via a build material formulation reservoir, which reservoir optionally includes a temperature control unit (e.g. a temperature sensor and/or a heating device) and a material level sensor. But that's fine. To dispense the build material formulation, a voltage signal is applied to the dispensing head such that droplets of the material formulation are selectively deposited through the dispensing head nozzle, such as in piezoelectric inkjet printing technology. applied. The ejection rate of each head depends on the number of nozzles, the type of nozzles, and the signal rate (frequency) of the applied voltage. Such ejection heads are known to those skilled in the art of solid freeform fabrication.

The total number of dispensing nozzles or nozzle arrays is such that half of the dispensing nozzles are designed to dispense the support material formulation and half of the dispensing nozzles are designed to dispense the build material formulation, i.e. Preferably, but not necessarily, the number of nozzles ejecting the formulation is selected to be the same as the number of nozzles ejecting the support material formulation. Four dispensing heads 16a, 16b, 16c, and 16d are shown in the exemplary embodiment of FIG. 1A. Each of heads 16a, 16b, 16c, and 16d has a nozzle array. In this example, heads 16a and 16b can be designed for build material formulations and heads 16c and 16d can be designed for support material formulations. Thus, head 16a may dispense a first build material formulation, head 16b may dispense a second build material formulation, and heads 16c and 16d both dispense a support material formulation. can do. In alternative embodiments, for example heads 16c and 16d may be combined into a single head having two nozzle arrays for dispensing the support material formulation.

Nevertheless, it is not intended to limit the scope of the invention, and the number of building material formulation dispensing heads (printing heads) and the number of support material formulation dispensing heads (supporting heads). It should be understood that the number may be different. Generally, the number of print heads, the number of support heads, and the number of nozzles in each head or head array are determined by the maximum delivery rate of the support material formulation and the maximum delivery rate of the build material formulation. is selected to provide a predetermined ratio α between the ratio α and the ratio α. Preferably, the value of the predetermined ratio α is selected to ensure that the height of the building material formulation in each layer formed is equal to the height of the support material formulation. Typical values for α are about 0.6 to about 1.5.

For example, if α=1, the total delivery rate of the support material formulation is approximately the same as the total delivery rate of the build material formulation when all the printing heads and support heads are operating.

In a preferred embodiment, there are M building heads each having m arrays of p nozzles and S support heads each having s arrays of q nozzles, so that M×m×p= It becomes S×s×q. Each of the M x m build arrays and the S x s support arrays can be manufactured as separate physical units that can be assembled into arrays and disassembled therefrom. . In this embodiment, each such array optionally and preferably includes its own temperature control unit and material formulation level sensor, and receives an individually controlled voltage for its operation. .

Apparatus 114 may further include a solidification device 324, which may include any device configured to emit light, heat, etc. that cures the deposited material formulation. For example, the solidification device 324 can include one or more radiation sources, such as ultraviolet or visible or infrared lamps, or other electromagnetic radiation sources, or electronic It can be a beam source. In some embodiments of the invention, solidification device 324 serves to harden or solidify the build material formulation.

In some embodiments of the invention, device 114 includes a cooling system 134, such as one or more fans.

The dispensing head and radiation source are preferably mounted on a frame or block 128 that preferably operates in reciprocating motion over a tray 360 that serves as a working surface. In some embodiments of the invention, the radiation source is mounted on the block such that the radiation source follows the dispensing head to at least partially cure or solidify the material formulation just dispensed by the dispensing head. It will be done. Tray 360 is arranged horizontally. In accordance with common convention, an XYZ Cartesian coordinate system is selected such that the XY plane is parallel to tray 360. Tray 360 is preferably configured to move vertically (along the Z direction), typically downwardly. In various exemplary embodiments of the invention, device 114 further includes one or more leveling devices 132, such as rollers 326. Leveling device 326 serves to straighten, level, and/or establish the thickness of a newly formed layer before the next layer is formed thereon. Leveling device 326 preferably includes a waste collection device 136 to collect excess material formulation generated during leveling. The waste collection device 136 may include some mechanism for delivering the material formulation to a waste tank or waste cartridge. More details on waste collection will be provided later.

In use, the dispensing heads of unit 16 move in a scanning direction, referred to herein as the X direction, selectively dispensing the build material formulation in a predetermined configuration as they pass over tray 360. Build materials typically include one or more support material formulations and one or more building material formulations. Following passage through the dispensing head of unit 16, curing of the building material formulation by means of radiation source 126 takes place. During the reverse passage of the head back to the starting point of the head for the just deposited layer, additional ejection of the build material formulation may be performed according to a predetermined configuration. During the forward or reverse passage of the dispensing head, the layer thus formed is straightened by a leveling device 326 which preferably follows the path of the dispensing head during forward and/or reverse movement of the leveling device. When the dispensing heads return to their starting point along the You can keep building. Alternatively, the ejection head may move in the Y direction between forward and reverse movements, or after two or more forward-reverse movements. A series of scans performed by a dispensing head to complete a single layer is referred to herein as a single scan cycle.

Once a layer is completed, the tray 360 is lowered in the Z direction to a predetermined Z level, depending on the desired thickness of the next printed layer. This procedure is repeated so that the three-dimensional object 112 is formed layer by layer.

In another embodiment, the tray 360 may be displaced in the Z direction during forward and reverse passes of the dispensing head of the unit 16 within the layer. Such a Z displacement is performed to bring the leveling device into contact with the surface in one direction and prevent contact in the other direction.

System 110 optionally and preferably includes a build material formulation supply system 330 that includes a build material formulation container or cartridge and supplies a plurality of build material formulations to manufacturing device 114.

Control unit 340 also controls manufacturing equipment 114 and optionally and preferably feed system 330 . Control unit 340 typically includes electronic circuitry configured to perform control operations. The control unit 340 is in communication with a data processor 154 that transmits digital data relating to fabrication instructions based on computer object data, e.g., a CAD configuration represented on a computer readable medium, such as in Standard Tessellation Language (STL) format. is preferred. Typically, control unit 340 controls the voltage applied to each jetting head or nozzle array and the temperature of the respective printhead's build material formulation.

Once the manufacturing data is loaded into the control unit 340, the control unit can operate without user intervention. In some embodiments, control unit 340 receives additional input from an operator, such as using data processor 154 or using user interface 116 in communication with unit 340. User interface 116 can be of any type known in the art, including, but not limited to, a keyboard, touch screen, and the like. For example, control unit 340 may receive as additional input the type and/or attributes of one or more build material formulations, such as color, property distortion, and/or transition temperature, viscosity, electrical properties, magnetic properties, etc. but not limited to. Other attributes and attribute groups are also possible.

Another representative, non-limiting example of a system 10 suitable for AM of objects according to some embodiments of the invention is shown in FIGS. 1B-1D. 1B-1D illustrate a top view (FIG. 1B), a side view (FIG. 1C), and an isometric view (FIG. 1D) of system 10.

In this embodiment, system 10 includes a tray 12 and a plurality of inkjet printheads 16, each having a plurality of separate nozzles. Tray 12 may have the shape of a disc or may be annular. Non-circular shapes are also contemplated, provided they can be rotated about a vertical axis.

Tray 12 and head 16 are optionally and preferably mounted to allow relative rotational movement between tray 12 and head 16. This is achieved by: (i) configuring the tray so that the tray 12 rotates about the vertical axis 14 relative to the head 16; and (ii) the head 16 rotates about the vertical axis 14 relative to the tray 12. or (iii) by configuring both tray 12 and head 16 to rotate about vertical axis 14 but at different rotational speeds (e.g., in opposite directions). can do. While the following embodiments will particularly focus on configuration (i) in which the tray is a rotating tray configured to rotate about the vertical axis 14 with respect to the head 16, this application will focus on configuration (ii). It should be understood that (iii) and (iii) are also contemplated. Any of the embodiments described herein can be adjusted to apply to any of configurations (ii) and (iii), and given the details described herein, how such adjustments are made. Those skilled in the art will understand.

In the following description, the direction parallel to the tray 12 and outward from the axis 14 will be referred to as the radial direction r, and the direction parallel to the tray 12 and perpendicular to the radial direction r will be referred to here as the azimuthal direction φ, which is perpendicular to the tray 12. This direction is called the vertical direction z here.

As used herein, the term "radial position" refers to a position on or above tray 12 that is a particular distance from axis 14. When the term is used in connection with a print head, it refers to the position of the head at a particular distance from axis 14. When the term is used in reference to a point on the tray 12, the term refers to any point belonging to the locus of points that describes a circle whose radius is at a certain distance from the axis 14 and whose center is on the axis 14. corresponds to

As used herein, the term "azimuthal position" refers to a position on or above tray 12 that is at a particular azimuth angle relative to a predetermined reference point. Therefore, a radial position refers to any point belonging to the locus of points that describe a straight line forming a particular azimuth angle with respect to a reference point.

As used herein, the term "vertical position" refers to the position across a plane that intersects the vertical axis 14 at a particular point.

Tray 12 serves as a support structure for three-dimensional printing. The work area in which one or more objects are printed is typically smaller than the total area of tray 12, but this need not be the case. In some embodiments of the invention, the working area is annular. The work area is indicated at 26. In some embodiments of the invention, the tray 12 rotates continuously in the same direction throughout the formation of the object, and in some embodiments of the invention, the tray 12 rotates at least once during the formation of the object. Reverse the direction of rotation (e.g. to vibrate). Tray 12 is optionally and preferably removable. Removal of the tray 12 may be performed for maintenance of the system 10 or, if desired, to replace the tray before printing a new object. In some embodiments of the invention, system 10 is provided with one or more different exchange trays (e.g., a kit of exchange trays), where the two or more trays have different types of objects (e.g., different weights), different movements. modes (e.g. different rotational speeds) etc. Tray 12 replacement can be manual or automatic as desired. If automatic exchange is employed, system 10 includes a tray exchanger 36 configured to remove tray 12 from its position beneath head 16 and replace it with a replacement tray (not shown). . In the representative view of FIG. 1B, the tray changer 36 is shown as a drive 38 with a movable arm 40 configured to pull the tray 12, although other types of tray changers are also contemplated.

An exemplary embodiment of printhead 16 is shown in FIGS. 2A-2C. These embodiments may be employed in any of the AM systems described above, including, but not limited to, system 110 and system 10.

2A-2B show printheads 16 with one (FIG. 2A) and two (FIG. 2B) nozzle arrays 22. FIG. Preferably, the nozzles in the array are arranged linearly along a straight line. In embodiments where a particular printhead has more than one linear nozzle array, the nozzle arrays may optionally and preferably be parallel to each other.

If a system similar to system 110 is used, all print heads 16 are optionally and preferably offset from each other in their position along the scanning direction and oriented along the indexing direction.

If a system similar to system 10 is used, all print heads 16 are optionally and preferably offset in their azimuthal positions from each other and oriented radially (parallel to the radial direction). Thus, in these embodiments, the nozzle arrays of the different print heads are not parallel to each other, but rather are at an angle to each other, with the angle approximately equal to the azimuthal offset between the respective heads. For example, one head may be radially oriented and placed at an azimuthal position φ ₁ , and another head may be radially oriented and placed at an azimuthal position φ ₂ . In this example, the azimuth offset between the two heads is φ ₁ -φ ₂ and the angle between the linear nozzle arrays of the two heads is also φ ₁ -φ ₂ .

In some embodiments, two or more printheads can be assembled into a block of printheads. In that case, the printheads of that block are generally parallel to each other. A block containing several inkjet printheads 16a, 16b, 16c is shown in Figure 2C.

In some embodiments, system 10 includes a support structure 30 positioned below head 16 such that tray 12 is between support structure 30 and head 16. Support structure 30 serves to prevent or reduce vibrations of tray 12 that may occur during operation of inkjet printhead 16. In configurations in which print head 16 rotates about axis 14, support structure 30 may also rotate (with tray 12 between head 16 and tray 12) such that support structure 30 is always directly beneath head 16. preferable.

Tray 12 and/or print head 16 are optionally and preferably moved parallel to vertical axis 14 along vertical direction z such that the vertical distance between tray 12 and print head 16 varies. It is composed of In configurations where the vertical distance is varied by moving the tray 12 along the vertical direction, it is preferred that the support structure 30 also move vertically with the tray 12. In configurations where the vertical position of the tray 12 remains fixed and the vertical distance is varied along the vertical direction by the head 16, the support structure 30 is also maintained at a fixed vertical position.

Vertical movement can be established by a vertical drive 28. Once a layer is completed, the vertical distance between tray 12 and head 16 can be increased by a predetermined vertical spacing depending on the desired thickness of the next printed layer (e.g., (lower the tray 12). This procedure is repeated so that the three-dimensional object 112 is formed layer by layer.

The orientation of inkjet printhead 16 and, optionally and preferably, the orientation of one or more other components of system 10, such as the orientation of movement of tray 12, is also controlled by controller 20. The controller can have an electronic circuit and a non-volatile storage medium readable by the circuit, the storage medium containing a program that, when read by the circuit, causes the circuit to perform control operations as further detailed below. Store instructions.

The controller 20 also supports, for example, standard tessellation language (STL) or stereolithography contour (SLC) formats, virtual reality modeling language (VRML), additive manufacturing file (AMF) formats, drawing exchange formats (DXF), polygon file formats. The host computer 24 may also communicate with the host computer 24 to transmit digital data relating to fabrication instructions based on computer object data in the form of (PLY) or any other format suitable for computer aided design (CAD). Object data formats are generally organized according to a Cartesian coordinate system. In such a case, computer 24 preferably performs a procedure to convert the coordinates of each slice in the computer object data from a Cartesian coordinate system to a polar coordinate system. Computer 24 optionally and preferably transmits fabrication instructions in a transformed coordinate system. Alternatively, the computer 24 can send the fabrication instructions in the original coordinate system provided by the computer object data, in which case the transformation of the coordinates is performed by the circuitry of the controller 20.

Transformation of coordinates allows three-dimensional printing on rotating trays. In conventional three-dimensional printing, the print head reciprocates along a straight line over a stationary tray. In such conventional systems, the print resolution is the same at any point on the tray, assuming uniform head firing rates. Unlike conventional three-dimensional printing, not all nozzles at a head point cover the same distance across tray 12 at the same time. A transformation of the coordinates is optionally and preferably performed to ensure equal amounts of excess material formulation at different radial positions. Representative examples of coordinate transformations according to some embodiments of the invention are presented in FIGS. 3A-3B showing three slices of an object (each slice corresponding to a fabrication order for a different layer of the object). . FIG. 3A shows the slices in a Cartesian coordinate system, and FIG. 3B shows the same slices after a coordinate transformation procedure has been applied to each slice.

Typically, controller 20 controls the voltages applied to each component of system 10 based on fabrication instructions and based on stored program instructions described below.

Generally, controller 20 controls print head 16 to eject droplets of build material formulation in layers to print a three-dimensional object on tray 12 during rotation of tray 12 .

System 10 optionally and preferably comprises one or more radiation sources 18, depending on the build material formulation used, for example ultraviolet or visible or infrared lamps, or other electromagnetic radiation sources. , or an electron beam source. The radiation source can include any type of radiation emitting device, including, but not limited to, light emitting diodes (LEDs), digital light processing (DLP) systems, resistive lamps, and the like. Radiation source 18 serves to harden or solidify the build material formulation. In various exemplary embodiments of the invention, the operation of radiation source 18 is controlled by controller 20, which can activate and deactivate radiation source 18, and optionally generate The amount of radiation used can also be controlled.

In some embodiments of the invention, system 10 further comprises one or more leveling devices 32, which can be manufactured as rollers or blades. The leveling device 32 serves to straighten the newly formed layer before the next layer is formed thereon. In some embodiments, the leveling device 32 has the shape of a conical roller and is arranged such that its axis of symmetry 34 is inclined to the surface of the tray 12 and its surface is parallel to the surface of the tray. Ru. This embodiment is shown in a side view of system 10 (FIG. 1C).

The conical roller can have the shape of a cone or a truncated cone.

The opening angle of the conical roller is preferably selected such that the ratio of the radius of the cone at any position along its axis 34 to the distance between that position and the axis 14 is constant. Since, while the roller rotates, every point p on the surface of the roller has a linear velocity that is proportional to (e.g., the same) the linear velocity of the tray at the point located vertically below point p, this embodiment Roller 32 allows for efficient leveling of the layers. In some embodiments, the roller has a truncated conical shape having a height h, a radius R ₁ at the closest distance from the axis 14, and a radius R ₂ at the farthest distance from the axis 14. Here the parameters h, R ₁ and R ₂ satisfy the relationship R ₁ /R ₂ = (R-h)/h, where R is the furthest distance of the roller from the axis 14 (e.g. R is (can be the radius of tray 12).

Operation of leveling device 32 is optionally and preferably controlled by controller 20. The controller can activate and deactivate the leveling device 32 and optionally adjust its position along the vertical direction (parallel to the axis 14) and/or in the radial direction (parallel to the tray 12). Its position along the axis 14 (toward or away from axis 14) can also be controlled.

In some embodiments of the invention, system 10 includes a cooling system (not shown, see FIG. 1A), such as one or more fans.

In some embodiments of the invention, print head 16 is configured to reciprocate relative to the tray along radial direction r. These embodiments are useful when the length of the nozzle array 22 of the head 16 is less than the radial width of the working area 26 on the tray 12. Movement of the head 16 along the radial direction is optionally and preferably controlled by a controller 20.

Some embodiments contemplate fabricating objects by dispensing different material formulations from different dispensing heads. These embodiments provide, among other things, the ability to select material formulations from a given number of material formulations and define desired combinations of selected material formulations and their properties. According to this embodiment, achieving the occupation of different three-dimensional spatial positions by different material formulations, or achieving the occupation of substantially the same three-dimensional position or adjacent three-dimensional positions by two or more different material formulations. The spatial location of the deposition of each material formulation in the layer is defined such that the post-depositional spatial combination of the material formulations within the layer is thereby defined, thereby allowing the composite material to be deposited at each location(s). It becomes possible to form a blend.

Any post-deposition combination or mixing of the build material formulations is contemplated. For example, after a particular material formulation is dispensed, it can maintain its original properties. However, when dispensed at the same time, at the same location, or in close proximity to another build material blend or other dispensed material blends, a composite material blend is formed that has different properties than the dispensed material blend. .

This embodiment thus allows the deposition of a wide range of combinations of material formulations and allows different parts of the object to be constructed from combinations of different material formulations, depending on the properties desired to characterize each part of the object. It makes it possible to create objects that can be used.

Further details of the principles and operation of an AM system suitable for this embodiment can be found in US Published Application No. 20100191360, the contents of which are incorporated herein by reference.

FIG. 4 provides a flowchart describing an exemplary method according to some embodiments of the invention.

Unless otherwise specified, it should be understood that the operations described below can be performed simultaneously or sequentially in many implementation combinations or orders. In particular, the order of flowchart illustrations should not be considered limiting. For example, two or more operations that appear in a flowchart illustration or in the description below in a particular order can be performed in a different order (eg, in reverse order) or substantially simultaneously. Furthermore, several operations described below are optional and may not be performed.

Computer programs implementing the methods of the present embodiments can generally be distributed to users on distribution media such as, but not limited to, floppy disks, CD-ROMs, flash memory devices, and portable hard drives. From the distribution medium, the computer program can be copied to a hard disk or similar intermediate storage medium. Computer programs can be executed by loading computer instructions from their distribution medium or their intermediate storage medium into an implemented storage device of a computer that configures the computer to operate according to the methods of the invention. All these operations are well known to those skilled in the art of computer systems.

The computer-implemented method of this embodiment can be implemented in many forms. For example, it can be implemented in a tangible medium such as a computer for performing the method operations. It can be implemented in a computer-readable medium that includes computer-readable instructions for performing the method operations. It may also be implemented on an electronic device having digital computer capability arranged to cause a computer program to be executed on a tangible representation medium or to cause instructions to be executed on a computer readable medium.

The method begins at 200 and optionally and preferably continues to 201, where computer object data in any of the formats described above is obtained. An exemplary technique for obtaining computer object data is described below with reference to FIGS. 18A and 18B.

The method continues at 202, where an uncured build material as described herein (e.g., one or more soft build material formulations as described herein, optionally as described herein) droplets of one or more elastomeric curable formulations, and optionally support material formulations, as described in 1. and layered onto a receiving medium, optionally and preferably using an AM system such as, but not limited to, system 110 or system 10. Dispensing 202 is optionally and preferably performed by at least two different multi-nozzle inkjet printheads. The receiving medium can be a tray (eg, tray 360 or 12) of an AM system as described herein, or a previously deposited layer.

The droplets are optionally and preferably ejected in a configuration pattern corresponding to a slice of an object having the shape of, or similar to, the shape of a body structure as defined herein.

In some embodiments of the invention, ejection 202 is performed under ambient conditions.

Optionally, the uncured build material, or a portion thereof (eg, one or more formulations of build material), is heated before being dispensed. These embodiments are particularly useful for uncured build material formulations that have relatively high viscosities at the operating temperatures of the 3D inkjet printing system work chamber. Preferably, the formulations are heated to a temperature that allows the respective formulation to be jetted through the nozzles of the print head of the 3D inkjet printing system. In some embodiments of the invention, the heating is to a temperature at which the respective formulation exhibits a viscosity of X centipoise or less. where X is about 30 centipoise, preferably about 25 centipoise, more preferably about 20 centipoise, or 18 centipoise, or 16 centipoise, or 14 centipoise, or 12 centipoise, or 10 centipoise, or even lower.

The heating is performed before filling the respective formulation into the print head of an AM (e.g. 3D inkjet printing) system, or while the formulation is in the print head, or while the composition passes through the nozzles of the print head. can be done.

In some embodiments, the heating is applied to each formulation into the ejection (e.g., inkjet printing) head to avoid clogging of the ejection (e.g., inkjet printing) head with the formulation if the viscosity of the formulation is too high. carried out before filling.

In some embodiments, the heating is performed by heating the ejection (e.g., inkjet printing) head at least while the building material formulation passes through the nozzles of the ejection (e.g., inkjet printing) head.

Once the uncured build material has been dispensed onto the receiving medium according to the computer object data (e.g. print data), the method optionally and preferably continues at 203 where the curing conditions (e.g. curing energy) are adjusted, e.g. applied to the deposited layer by a radiation source as described herein. Preferably, curing conditions are applied to each individual layer after deposition of the layer and before deposition of the previous layer.

In some embodiments, the application of curing conditions is performed under a substantially dry, inert environment, as described herein.

The method ends at 204.

In some embodiments, the method is practiced using an exemplary system as described herein in any of the respective embodiments and any combination thereof.

The build material formulations can be contained in a particular container or cartridge of the solid freeform fabrication device, or in a combination of build material formulations deposited from different containers of the device.

In some embodiments, at least one, or at least two or three (e.g., at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 80, or more), or all The layer is formed by ejection of a droplet, such as in a single soft build material formulation 202, as described herein in any of the respective embodiments.

In some embodiments, at least one, or at least two or three (e.g., at least 10, at least 20, at least 30, at least 40, at least 50, at least 60, at least 80, or more), or all The layers may include two or more build material formulations, each from a different ejection (e.g., inkjet printing) head, as in 202, as described herein in any of the respective embodiments. It is formed by ejecting droplets.

These embodiments specifically provide the ability to select materials from a predetermined number of materials and define desired combinations of the selected materials and their properties. According to this embodiment, the spatial location of the deposition of each material in the layer may implement the occupation of different three-dimensional spatial locations by different materials, or substantially the same three-dimensional location or The occupation of adjacent three-dimensional locations is defined to enable subsequent deposition spatial combination of materials within layers, thereby forming a composite material at each location.

Any subsequent deposition combination or mixing of the building materials is contemplated. For example, once a material is dispensed, it can retain its original properties. However, when it is dispensed simultaneously with another build material or other dispensed materials that are dispensed at the same or adjacent location, a composite material is formed that has different properties than the dispensed material.

Some of the embodiments enable the dispensing of a wide range of material combinations and the fabrication of objects that can be comprised of a plurality of different material combinations in different parts of the object according to desired properties to characterize each part of the object. do.

In some of these embodiments, the two or more build material formulations are dispensed in a voxel fashion, and a voxel of one of the build material formulations is a voxel of at least one other build material formulation. interlaced with the voxels of the formulation.

Some embodiments provide methods of layered fabrication of three-dimensional objects, in which at least two or three (e.g., at least 10, at least 20, at least 30, at least 40, or at least 80) layers or all For each layer, two or more build material formulations are optionally and preferably dispensed using system 10 or system 110. Preferably, each build material formulation is dispensed by jetting it from a plurality of nozzles of a print head (eg, head 16). The dispensing is done in a voxel fashion, wherein voxels of one type of the building material formulation are interlaced with voxels of at least one other type of building material formulation according to a predetermined voxel ratio.

Such a combination of two building material formulations at a predetermined voxel ratio is referred to as a digital material (DM). A representative example of a digital material is shown in FIG. 5, which shows materials A and B interlaced over areas of the layer in a voxel fashion.

In some embodiments, the ejection of two build material formulations at predetermined voxel ratios is performed for composite structures made from a soft material formulation and an elastomeric curable formulation as described in the example below. This makes it possible to obtain materials with desired mechanical properties, such as those exemplified in the section.

For any predetermined ratio of materials, digital materials can be formed, for example, by ordered or disordered interlacing. Embodiments are also contemplated in which the interlacing is semi-chaotic (eg, a repeating pattern of sub-regions, each sub-region comprising a chaotic interlacing).

In some embodiments of the invention, the interlaced locations occupied by one of the formulations constitute about 10% to about 30% or about 15% to about 25% of the area of the layer. These embodiments are particularly useful when one of the materials is a soft build material formulation as described herein and the other material is a curable formulation as described herein. The interlaced locations useful, in which case occupied by the elastomeric curable formulation, optionally and preferably comprise about 10% to about 30% or about 15% to about 25% of the area of the layer. Configure.

In some embodiments of the invention, voxel elements comprising one of the formulations form a capacitive fiber pattern in the object. These embodiments may be implemented when one of the materials is a soft build material formulation as described herein and the other material is an elastomeric curable formulation as described herein. Particularly useful are voxel elements comprising elastomeric curable formulations forming capacitive fiber patterns in the object. The fiber thickness characteristic of the fiber pattern is, but is not limited to, about 0.4 mm to about 0.6 mm.

The fiber pattern can be perpendicular to the plane of the layer, or more preferably, although not necessarily, oblique to the plane of the layer. The diagonal fiber pattern is optionally and preferably substantially parallel (e.g., offset by less than 10°) to the tear force applied by a roller (e.g., roller 326 or 32) on the layer during the straightening operation. ). Representative examples of fiber pattern directions include, but are not limited to, angles from about 30° to about 60°, such as about 45°, relative to the plane.

As part of any of the embodiments described herein, droplets of two or more build material formulations are ejected in each of at least two or three layers as described herein. When applied, the discharge is such as to form a core region and one or more envelope regions at least partially surrounding said core region. Such extrusion results in the fabrication of an object consisting of a plurality of layers, a layered core constituting the core region and a layered sheath constituting the envelope region.

In some embodiments of the invention, the sheath is formed from an elastomeric curable formulation as described herein. Optionally and preferably, the sheath can be removed after completion of additive manufacturing of the three-dimensional object.

The structure according to some of these embodiments is a sheath-like structure made of two or more curable materials. The structure generally includes a layered core that is at least partially covered by one or more layered sheaths such that at least one layer of the core engages at least one layer of the sheath in the same plane.

The thickness of each sheath, measured perpendicular to the surface of the structure, is generally at least 10 μm. In various exemplary embodiments, the core and sheath differ from each other in their thermomechanical properties. This is easily accomplished by fabricating the core and sheath from different build material formulations or a combination of different build material formulations. The thermomechanical properties of the core and sheath are referred to herein as "core thermomechanical properties" and "sheath thermomechanical properties," respectively.

Representative, non-limiting examples of structures according to some embodiments of the invention are shown in FIGS. 6A-D.

6A is a schematic diagram of a perspective view of structure 60, and FIG. 6B is a cross-sectional view of structure 60 along line AA of FIG. 6A. A Cartesian coordinate system is also shown for clarity of presentation.

Structure 60 includes multiple layers 62 stacked along the Z direction. Structure 60 is typically fabricated by AM techniques, such as using system 10 or system 110, whereby the layers are formed in a continuous manner. Therefore, the Z direction is also referred to herein as the "build direction" of the structure. Layer 62 is therefore perpendicular to the construction direction. Although structure 60 is shown as cylindrical, this need not be the case. This is because the structure of this embodiment can have any shape.

The sheath and core of structure 60 are indicated at 64 and 66, respectively. As shown, the layers of core 66 and sheath 64 are coplanar. AM technology allows simultaneous fabrication of the sheath 64 and core 66 such that for a particular formed layer, the inner portion of the layer constitutes the layer of the core and the periphery of the layer or a portion thereof Makes up the layers of the sheath.

The peripheral area of the layer that contributes to the sheath 64 is referred to herein as the "envelope region" of the layer. In the non-limiting example of FIGS. 6A and 6B, each of layers 62 has an envelope region. That is, each layer in Figures 6A and 6B contributes to both a core and a sheath. However, this does not necessarily have to be the case. This is because for some applications it may be desirable for the wick to be exposed to the environment in some areas. In these applications, at least a portion of the layer does not include an envelope region.

A representative example of such a configuration is shown in the cross-sectional view of FIG. 6C, which shows that some layers 68 contribute to the core rather than the sheath, and some layers 70 contribute to both the core and the sheath. has been done. In some embodiments, one or more layers do not include regions with core thermomechanical properties and only include regions with sheath thermomechanical properties. These embodiments are particularly useful when the structure has one or more thin sections, where the layers forming those portions of the structure are preferably devoid of core regions. Embodiments are also contemplated in which one or more of the layers does not include regions with sheath thermomechanical properties, but only includes regions with core thermomechanical properties.

The sheath may also optionally and preferably cover the structure 60 from above and/or from below with respect to the Z direction. In these embodiments, some of the layers at the top and/or bottom portions of structure 60 have at least one material property that is different from core 66. Various exemplary embodiments of the invention provide that the top and/or bottom portions of structure 60 have the same material properties as sheath 64. A representative example of this embodiment is shown in Figure 6D. The upper/lower sheath of structure 60 may be thinner (eg, twice as thin) than the side sheaths. This may be the case, for example, when the upper or lower sheath contains the upper or lower layer of the structure and therefore has the same thickness as required for the layers forming the object.

In some embodiments of the invention, the core is made from a soft modeling compound as described herein in any of the respective embodiments, and the sheath is made from a soft modeling compound as described herein in any of the respective embodiments. Made from elastomeric curable formulations as described herein.

In some embodiments of the invention, both the core and sheath are DM materials.

In some embodiments of the invention, the core comprises a soft building compound, e.g., as described herein in any of the respective embodiments, and as described herein in any of the respective embodiments. The sheath includes a DM material made from an elastomeric curable formulation as described herein, and the sheath is made from an elastomeric curable formulation as described herein in any of its respective embodiments.

Whenever "soft material formulations" or "elastomeric curable formulations" are described, formulation systems containing the same are contemplated.

When both the core and sheath are made from DM comprised of the same build material formulation, the relative surface density of either build material in the core is the relative surface density of that material in the sheath or mantle region. It is different from. However, in some embodiments, the core is formed from DM and the sheath is formed from a single type of building material formulation, or vice versa.

In various exemplary embodiments of the invention, the thickness of the sheath, measured in the XY plane (perpendicular to the construction direction Z), is non-uniform across the construction direction. In other words, different layers of the structure can have envelope regions of different widths. For example, the thickness of the sheath along a direction parallel to the X-Y plane can be calculated as a percentage of the diameter of each layer along that direction, thus making the thickness dependent on the size of the layers. let In various exemplary embodiments of the invention, the thickness of the sheath is non-uniform across a direction that is tangent to the outer surface of the sheath and perpendicular to the construction direction. Regarding the layers of the structure, these embodiments correspond to envelope regions with widths that are non-uniform along the circumference of each layer.

In some embodiments of the invention, the sheath of the structure, or a portion thereof, is a "sheathed" structure that includes a sheath region alone and another. In particular, in these embodiments, the structure includes an inner core at least partially surrounded by at least one intermediate jacket region, and the intermediate jacket is surrounded by an outer jacket region. Measured perpendicular to the construction direction, the thickness of the intermediate mantle region is optionally and preferably greater than the thickness of the outermost mantle region (eg, 10 times or more greater). In these embodiments, the intermediate mantle region serves as a structural sheath and therefore has sheath characteristics as further detailed above. The outermost jacket sheath may also serve to protect the middle jacket from breaking under load.

The structure of this embodiment, as mentioned, can be formed in a layered manner, for example using the system 10 or 100 described above. In various exemplary embodiments of the invention, computer-implemented methods automatically perform dynamic adaptation of the sheath to specific elements of the structure. The method may optionally and preferably use user input to calculate a sheath for each region of the structure and assign voxels of the outer surface to respective build materials or combinations of build materials. . The computer-implemented method can be performed by a control unit (eg, control unit 152 or 20, see FIGS. 1A and 1B) that controls the solid freeform fabrication apparatus by a data processing device (eg, data processing device 154 or 24).

In some embodiments of the invention, one or more additional sheath layers are dispensed to also form a sheath at the top and/or bottom portions of the structure. Preferably, these layers lack a core region. Because they serve to take out the wick from above or from below. When it is desired to core from the top, an additional sheath layer is dispensed on top of all other layers, and when it is desired to core from the bottom, an additional layer is deposited on the work surface (e.g. tray 360 or 12, FIG. 1A and 1B), while all other layers are subsequently deposited.

Any of the envelope regions optionally has a width of at least 10 μm. Preferably all envelope regions have a width of at least 10 μm. Any of the core and jacket regions, and optionally the top and/or bottom additional layers, may be made of a build material formulation or combination of build material formulations as described herein (e.g. digital material).

In some embodiments of the invention, the sheath is selectively fabricated in different regions of the structure to change the mechanical properties only in selected region areas without affecting the mechanical properties in other regions. Ru.

In some parts of any of the embodiments of the invention, once the layer is dispensed as described herein, exposure to curing energy as described herein is performed. In some embodiments, the curable material is a UV curable material and the curing energy is such that the radiation source emits UV radiation.

In some embodiments, if the build material also includes a support material formulation, the method involves removing the support material formulation. This can be carried out by mechanical and/or chemical means, as recognized by those skilled in the art.

FIG. 18A is a flowchart diagram of an exemplary method that may be used according to some embodiments of the invention to perform operation 201 above. The method is particularly useful for obtaining computer object data for use in system 10 or system 110. Unless otherwise specified, it should be understood that the operations described below can be performed simultaneously or sequentially in many implementation combinations or orders. In particular, the order of flowchart illustrations should not be considered limiting. For example, two or more operations that appear in a flowchart illustration or in the description below in a particular order can be performed in a different order (eg, in reverse order) or substantially simultaneously. Furthermore, several operations described below are optional and may not be performed.

The method begins at 700 and optionally and preferably continues at 701, where data in a format suitable for Digital Imaging and Communications in Medicine (hereinafter DICOM data) is received.

DICOM data includes MRI systems, CT imaging systems, helical CT systems, positron emission tomography (PET) systems, 2D or 3D fluoroscopy systems, 2D, 3D or 4D ultrasound imaging systems, endoscopy systems, and bedside monitoring systems. , X-ray systems, and hybrid imaging systems of CT, MR, PET, ultrasound, or other imaging techniques. DICOM data preferably includes one or more digital image data describing one or more body structures, including one or more body tissues and/or organ elements.

In some embodiments of the invention, the DICOM data preferably includes one or more digital image data describing one or more soft tissues, or organs or systems comprising soft tissues; In some implementations of the present invention, DICOM data preferably includes one or more digital image data describing one or more body structures including one or more body organs and/or tissue elements other than soft tissue. In the form, DICOM data preferably includes one or more digital image data describing one or more body soft tissues and one or more body organs and/or one or more body organs including tissue elements other than soft tissue. Contains one or more digital image data describing the structure.

The method optionally and preferably continues at 702, where the DICOM data is converted to computer object data. For example, computer object data may be in standard tessellation language (STL) or stereolithography contour (SLC) format, virtual reality modeling language (VRML), additive manufacturing file (AMF) format, drawing exchange format (DXF), polygon file format (PLY), or any other format suitable for computer-aided design (CAD). Conversion of DICOM data to computer object data optionally and preferably includes one or more segmentation methods selected from the group consisting of thresholding, region forming methods, dynamic region forming methods, and the like.

Thresholding methods exploit differences in the density of different tissues to select image pixels with values equal to or greater than a defined threshold. For example, the defined threshold of the thresholding method can be selected such that image pixels relating to hard tissue pass the thresholding method and other image pixel associations are filtered out. The thresholding method can be applied multiple times each time using different thresholds to obtain separate data sets for different tissue types.

Region forming methods are generally applied after thresholding to separate regions with the same concentration range. The region forming method can examine neighboring pixels of an initial seed point and determine whether the neighboring pixels belong to the region. The method is optionally and preferably performed iteratively to segment the image. For example, seed points can be selected according to different tissue types, and region-forming segmentation techniques can be performed iteratively to isolate image pixels that belong to one of these tissue types. can. In dynamic region formation methods, regions of image parameters are selected in addition to seed points. These parameters are chosen to allow recognizing the same image pixels as the seed points.

Typically, but not necessarily, an initial background segmentation method is applied to remove from DICOM data elements that do not belong to any of the tissue types of interest. Subsequent segmentation methods can be applied for more refined segmentation of one or more refined regions of the target anatomy by using different segmentation techniques.

After segmentation, converting DICOM data to computer object data may also include smoothing, wrapping, and/or hole filling to compensate for artifacts in the DICOM data. Format conversion methods can then be applied to the segmented DICOM data to provide computer object data in any of the above-mentioned formats.

In some embodiments of the invention, input data is received from a computer readable medium as computer object data, in which case there is no need to obtain and convert DICOM data. In these embodiments, it is not necessary to perform operations 701 and 702.

In any event, the computer object data preferably includes data regarding the shape of one or more body structures including one or more body tissue elements as further detailed above. The computer object data, whether obtained by conversion of DICOM data or directly received as such, is optionally and preferably arranged into multiple files, each relating to a different body structure.

At 703, the type of body structure mimicked by the additively manufactured object (e.g., soft tissue, muscle tissue, smooth tissue, bone tumor, cartilage, intervertebral disc, nerve/spinal cord, fluid duct) is determined for each data file. be done. The determination may be made by extracting information present in each computer object data file, or each DICOM data file, or information associated with each data file.

At 704, a set of rules associated with each body structure is selected. This set of AM rules optionally and preferably includes the build material formulation to be dispensed, as well as the dispensing parameters and conditions (eg, temperature, interlacing ratio, interlacing texture). This set of AM rules can be obtained from a look-up table having an input for each type of body structure and a set of parameters associated with each such input. In some embodiments of the invention, a subject profile is received. Subject profiles typically include weight, gender, age, ethnicity, ancestry, medical history, etc. In some embodiments of the invention, the subject profile also includes a genetic profile, which can include genes throughout the subject's genome, or it can include a particular subset of genes. Genetic profiles can include genomic profiles, proteomic profiles, epigenomic profiles, and/or transcriptomic profiles. In embodiments where a subject profile is received, the lookup table also includes inputs for different profile parameters. In particular, the lookup table may include multiple entries for each type of body structure, one entry for each profile parameter. As a representative, non-limiting example, the look-up table may include multiple entries for soft tissue structures, one entry for each age group.

In some embodiments of the invention, the set of AM rules is selected by an operator, eg, via a user interface (eg, user interface 116). Embodiments in which both look-up tables and user interfaces are used are also contemplated. For example, a lookup table can be used to reduce the number of choices given to the operator, and a user interface can be used to select the final set of AM rules.

Furthermore, embodiments are contemplated in which a set of rules is received along with computer object data. For example, each computer object data file can include one or more AM rules, or can be associated with an AM rules file that includes one or more AM rules, where the AM rules are associated with each computer object data file. handle.

At 705, a slicing operation is optionally and preferably applied to each computer object data file separately. Slicing typically describes a 2D voxel map of each plane (the plane corresponds to a layer of the object mimicking the respective body structure) characterized by a different vertical coordinate (e.g. the z coordinate mentioned above). This is accomplished by generating a set of image files to a computer object data file. The image file can be in any 2D format known in the art, such as, but not limited to, a bitmap file (BMP), portable network graphics (PNG), and the like. A preferred slicing technique is provided below with reference to FIG. 18B.

At 706, two or more sets of image files are combined into a single image file. For example, combining image files that correspond to objects that correspond to the same vertical coordinates but that mimic different body structures will result in slices of two or more objects, each of which mimics two or more body structures, once printed. An image file can be provided that describes the layers containing the areas. At 707, the image file is uploaded to an AM system, such as, but not limited to, system 10 or system 110 to fabricate a non-living object that resembles a body structure.

The method ends at 708.

FIG. 18 is a flowchart diagram of an exemplary slicing method according to some embodiments of the invention. This method is particularly useful for implementing slicing operation 705 of FIG. 18A. The method begins at 720 and is optionally and preferably applied to each voxel in the computer object data.

In decision 721, a distance field value for the 3D object is determined for each voxel. The distance field value indicates whether the voxel is inside or outside the object that mimics the body structure being printed. For example, a negative distance field value is assigned to voxels outside the object that mimics body structure, a positive distance field value is assigned to voxels inside the object that mimics body structure, and a zero distance field value is It can be assigned to voxels on the outermost surface of an object that mimic body structure. A representative example of a suitable technique for determining distance field values is given in Example 5 below.

When the voxel is within or on the outermost surface of the object that mimics body structure (e.g., when the distance field value is positive), the method continues at 722 where the build material formulation is Assigned to each voxel. The build material formulation may be a building material formulation, such as a soft building material formulation or formulation system containing the same, an elastomer curable formulation or formulation system containing the same, or a formulation or formulation system thereof. (any combination), support material formulation, or liquid material formulation, optionally and preferably based on the position of the voxel in the 3D object, and the AM rules obtained in 704 above. It is determined. From 722, the method continues to 724, where the method selects pixel values that correspond to the assigned build material formulation. A pixel value can be any value that is uniquely representative of the assigned build material formulation. For example, pixel values can be grayscale levels or color values (eg, RGB values).

When the voxel is outside the object that mimics body structure (e.g., when the distance field value is negative), the method continues to a determination 723 where the method determines whether the voxel should be occupied or left blank. Decide what should be. If the voxel is to remain blank, the method continues at 726, where the method selects a pixel value that uniquely represents a blank pixel. For example, the method can select null values to represent blank pixels. Alternatively, when the voxel is outside the object that mimics the body structure, the method continues from 723 to 728, where it ends. Pixels that are not assigned any value in that case should be considered as an instruction to blank the voxel.

If the voxel is occupied, the method continues at 725 where a build material is assigned to the voxel and then continues at 724 where the method assigns the assigned build material formulation as further detailed above. Select the corresponding pixel value.

From 724, 725 or 726, as the case may be, the method continues to 727 where the selected pixel value is assigned to the pixel in the 2D image, where the position of the pixel in the 2D image is determined by the position of the pixel in the layer represented by the 2D image. Corresponds to the voxel position.

The method ends at 728.

Throughout this specification, the term "body" as used in the context of, e.g., structure, organ, tissue or material, refers to a structure, organ designated as being part of the body of a subject, preferably a living subject. , describe the organization or material. This term encompasses biological systems, organs, tissues, cells and materials.

Throughout this specification, the term "subject" encompasses animals of any age, preferably mammals, and more preferably humans. The term encompasses individuals who are at risk of developing or suffering from the disease.

The term "body structure" refers to a part of a subject's body, including systems, organs, tissues, cells, and the surrounding environment of any of them, as described herein. Body structures can include, for example, multiple organs that work together in an organism, such as the gastrointestinal tract, cardiovascular system, respiratory tract, and the like. Structures can include organs and tissues that form part of these systems, as well as structures associated with pathological conditions, such as tumor cells or tissues. The body structure may alternatively include, for example, the heart and its associated blood vessels. The body structure may alternatively include an organ such as an arm or forearm, or a leg, with associated bone and muscle tissue, vasculature, tumor tissue (if present) and/or its surroundings. Skin tissue can be included.

The term "tissue" describes a part of an organism consisting of cells designed to perform a function or functions. Examples include brain tissue, retina, skin tissue, liver tissue, pancreatic tissue, bone, cartilage, connective tissue, vascular tissue, muscle tissue, heart tissue, vascular tissue, kidney tissue, lung tissue, gonadal tissue, and hematopoietic tissue. including but not limited to.

Soft modeling material formulation:
Build material formulations that can be used in the additive manufacturing methods described herein in any of the respective embodiments have a Shore A hardness of less than 10 or a Shore OO hardness of less than 40 when cured. at least one building material formulation (shown, characterized). Such formulations are also referred to herein as "soft material formulations" or "soft material building formulations" or "soft building formulations."

"Hardness" herein and in the industry describes resistance to permanent indentation when measured under specified conditions. Shore A hardness, also referred to as hardness ShA or Shore Scale A hardness, is determined according to the ASTM D2240 standard using a digital Shore A durometer. Shore OO hardness, also referred to as hardness ShOO or Shore scale OO hardness, is determined according to the ASTM D2240 standard using a digital Shore OO hardness durometer. D, A, and OO are common measures of hardness values, each measured using a respective durometer. FIG. 7 provides Shore hardness values at different scales for exemplary common materials.

In some of any of the embodiments described herein, the soft material formulation described herein has a Shore A hardness in the range of 0 to about 10 when cured; It includes any intermediate values and subranges therebetween.

In some of any of the embodiments as described herein, the soft material formulation described herein, when cured, has a Shore OO hardness ranging from 0 to about 20, or such as from about 10 to about 20, or from about 10 to about 30, including any intermediate values and subranges therebetween.

Another parameter that indicates the low hardness of the resulting soft material for cured soft material formulations as described herein is the compressive modulus.

As used herein, "compressive modulus" refers to the ratio of mechanical stress to strain in a material when the material is compressed. Compressive modulus can also be viewed as the modulus of elasticity imparted to a material under compression. In some embodiments, the compression ratio is determined according to ASTM D695. In some embodiments, the compressive modulus is determined as described in the Examples section below and is 40 when measured in compressive mode, taken at strain values between 0.001 and 0.01. It can be expressed as compressive stress in % strain or as the slope of the stress versus strain curve.

In some of any of the embodiments described herein, the soft material formulation as described herein has a compressive modulus of at least 0.01 MPa when cured.

In some embodiments, the soft material formulations as described herein, when cured, have a pressure of about 0.01 to about 0.2 MPa, or about 0.02 to about 0.2 MPa, or about has a compressive modulus (as defined herein) of 0.01 to about 0.1 MPa, or about 0.02 to about 0.1 MPa, or about 0.03 to about 0.07 MPa, which including intermediate values and subranges therebetween.

In some embodiments, a soft material formulation as described herein, when cured, has at least moderate tear resistance in addition to its low hardness.

Tear resistance (TR) describes the force required to tear a material, which force acts substantially parallel to the major axis of the sample. Tear resistance, as measured by the ASTM D412 method, can be used to measure resistance to tear formation (tear initiation) and resistance to tear propagation (tear propagation). Generally, the sample is held between two holders and a uniform tensile force is applied until deformation occurs. Tear resistance is then calculated by dividing the applied force by the thickness of the material. Materials with low tear resistance tend to have poor resistance to abrasion.

In some embodiments, tear resistance is determined as described in the Examples section below.

In some of any of the embodiments described herein, the soft material formulation described herein, when cured, has a It has a tear resistance of at least 100 N/m.

In some embodiments, the soft material formulation as described herein, when cured, has a tear resistance of at least 150 N as determined by ASTM D624 for a specimen having a thickness of 2 mm. , in some embodiments, it has a tear resistance of 150 N/m to 500 N/m, or 150 to 400 N/m, or 200 N/m to 400 N/m, or 200 N/m to 350 N/m, and it , including any intermediate values and subranges therebetween.

In some embodiments, tear resistance measurements are used to determine the time to failure of a specimen under an applied tensile force.

In some embodiments, the soft material formulation as described herein, when cured, exhibits a hardness of at least 9 seconds, such as between 9 and 50 seconds, as measured by ASTM D624 on a specimen having a thickness of 2 mm. , or 9 to 40 seconds, or 9 to 30 seconds, or 15 to 30 seconds.

In some of the embodiments as described herein, the soft building compounds as described herein have good reactivity, i.e., the dispensed layer containing the formulation , cured when exposed to curing conditions in a time period of less than 1 second, and/or a cured layer made from a soft building compound (e.g., as shown in the Examples section below). ) It has the characteristic of exhibiting good adhesion.

In some embodiments, a soft building compound as described herein is characterized by a transition from liquid to solid within 1 second upon exposure to curing conditions. In some of these embodiments, the curing condition is UV radiation, for example UV radiation at 1 W/ ^cm2 . In some embodiments, the UV radiation is a UV mercury (Hg) arc lamp (medium pressure, metal halide). In some embodiments, a soft building compound as described herein is cured under curing conditions (e.g., a 250W mercury arc lamp at a wavelength of about 300 nm to about 450 nm and a power density of about 1 W/ ^cm2). It is characterized by a transition from liquid to solid within 1 second upon exposure to UV irradiation (using UV radiation).

The time required for liquid to solid transition can be determined using conventionally known DSC measurements.

In part of any of the embodiments described herein, a soft build material formulation as described herein has good compatibility with an AM system, i.e., it has characterized by meeting system operating conditions (with respect to viscosity and viscosity stability, thermal stability, etc.).

In part of any of the embodiments described herein, a soft build material formulation as described herein has good compatibility with AM, 3D inkjet printing, i.e., it jettable, compatible, and of a viscosity suitable for use in an inkjet printhead as described herein, and at 25-75° C. for at least 24 hours, preferably at least 48 hours. It is characterized by having a viscosity stability of

In some of any of the embodiments as described herein, the soft building material formulation as described herein is maintained for at least 1 month, or at least 2, 3, 4, 5 months. and further stability (storage stability) of at least 6 months, i.e. by the formulation having substantially the same properties (e.g. any of the properties described herein) upon storage for the indicated time. characterized.

In some of any of the embodiments described herein, the soft building material formulation as described herein is maintained for at least 1 month, or at least 2, 3, 4, 5 months, and even is characterized by a stability (storage stability) of at least 6 months, ie, the formulation has substantially the same appearance (eg, color) upon storage (eg, room temperature) for the indicated time.

In some of any of the embodiments described herein, the soft building material formulation as described herein is a curable formulation; is curable by including a material that is polymerizable when exposed to curing conditions (eg, curing energy) as described herein. As described in more detail below, not all of the materials in a curable formulation should be curable to make the formulation curable. Thus, throughout this specification, with respect to any formulation described herein, the formulation is intended to be polymerizable when at least one of the materials in the formulation is curable or when exposed to curing conditions. Sometimes defined as being curable.

Throughout this specification, a "curable (hardenable) material" refers to a material that solidifies or solidifies (e.g., cures) when exposed to curing conditions (e.g., curing energy), as described herein. The compound forming the material (generally a monomeric or oligomeric compound, but optionally a polymeric material). A curable material is generally a polymerizable material that undergoes polymerization and/or crosslinking when exposed to suitable curing conditions (eg, an energy source).

Curable materials according to this embodiment also include materials that harden or solidify (cure) without exposure to curing energy, but rather to curing conditions (eg, exposure to chemical agents) or simply upon exposure to an environment.

As used herein, the terms "curable" and "curable" are interchangeable.

According to some embodiments of the invention, curable materials as described herein solidify upon undergoing polymerization and are referred to herein as polymerizable materials.

The polymerization can be, for example, free radical polymerization, cationic polymerization, or anionic polymerization, each of which involves exposure to curing energy or curing conditions other than curing energy, such as radiation, heat, etc., as described herein. can be induced.

In some of any of the embodiments described herein, the curable material is a photopolymerizable material, which polymerizes upon exposure to radiation, as described herein. , and/or undergo crosslinking, and in some embodiments, the curable material is a UV curable material, which is exposed to UV or UV-vis radiation, as described herein. When exposed, it polymerizes and/or undergoes crosslinking.

In some embodiments, a curable material as described herein is a photopolymerizable material that polymerizes via light-induced free radical polymerization. Alternatively, the curable material is a photopolymerizable material that polymerizes by photoinduced cationic polymerization.

In some of the embodiments described herein, the curable material can be a monomer, oligomer, or short chain polymer, each capable of being polymerized as described herein. and/or crosslinkable.

In some of the embodiments described herein, when the curable material is exposed to curing conditions (e.g., radiation), it hardens (by any one or a combination of chain extension and crosslinking). harden, solidify).

In some of the embodiments described herein, the curable material forms a polymerized or copolymerized material in a polymerization or copolymerization reaction when exposed to conditions (e.g., curing energy) that cause the polymerization reaction to occur. A monomer or a mixture of monomers that can be used. Such curable materials are also referred to herein as monomer curable materials.

In some of the embodiments described herein, the curable material is polymerized or copolymerized in a polymerization or copolymerization reaction when exposed to curing conditions (e.g., curing energy) in which the polymerization or copolymerization reaction occurs. An oligomer or mixture of oligomers that can form a polymeric material. Such curable materials are also referred to herein as oligomeric curable materials.

In some of the embodiments described herein, the curable material may be a monofunctional curable material or a multifunctional curable material, whether monomeric or oligomeric. can.

As used herein, a monofunctional curable material includes one functional group that can undergo polymerization when exposed to curing energy (eg, radiation).

Multifunctional curable materials contain two or more, such as two, three, four or more, functional groups that can undergo polymerization when exposed to curing energy. Multifunctional curable materials can be, for example, difunctional, trifunctional or tetrafunctional curable materials, which each contain two, three or four groups capable of undergoing polymerization. Two or more functional groups in a multifunctional curable material are linked together by a linking moiety, generally as defined herein. When the linking moiety is an oligomeric or polymeric moiety, the multifunctional group is an oligomeric or polymeric multifunctional curable material. Multifunctional curable materials can undergo polymerization and/or act as crosslinkers when subjected to curing energy.

According to some of any of the embodiments described herein, the formulation is a synthetic, non-living formulation and consists essentially of synthetic materials.

The term "synthetic material" as used herein describes materials that are not naturally present in living subjects, generally organic materials. The term encompasses non-living (eg, organic) materials, non-naturally occurring (eg, organic) materials, and/or synthetically produced (eg, organic) materials.

According to some of any of the embodiments described herein, the formulation is devoid of biological material.

As used herein, "biological material" refers to materials that are naturally present in living subjects, generally organic materials, as described herein. Such organic materials include, for example, cells and cell components, proteins (enzymes, hormones, receptors, ligands, etc.), peptides, nucleic acids, genes, amino acids.

"Lacking" means less than 1%, or less than 0.5%, or less than 0.1%, or less than 0.05%, or less than 0.01%, or 0.005% of the total weight of the formulation. means less than, or less than 0.001%, and less than these (including zero).

It should be understood that part of this invention contemplates formulations that include water.

According to some of any of the embodiments described herein, the formulation is non-cellularized, ie, devoid of biological cells or cellular components.

According to some of the embodiments described herein, the formulation has an amount of less than 10% by weight, or less than 8% by weight, or less than 5% by weight, or even less by weight. or devoid of water as defined herein.

According to some of any of the embodiments described herein, the formulation is such that it does not form a hydrogel when exposed to curing conditions.

As used herein and in the industry, the term "hydrogel" describes a material that includes a three-dimensional fibrous network as the solid phase and further includes an aqueous solution entrapped within the fibrous network.

Any formulation with Shore hardness as indicated, preferably combined with one or more, preferably all, of the other features described herein may be used in the additive manufacturing process described herein. planned.

According to some of any of the embodiments described herein, the soft build material includes a combination of curable and non-curable polymeric materials.

As used herein, "non-curable" with respect to a material in a soft formulation means that the material does not solidify when exposed to curing conditions that would solidify a curable material. The non-curable material may lack polymerizable and/or crosslinkable groups or may contain polymerizable and/or crosslinkable groups, but the polymerization and/or crosslinking may occur under curing conditions in which the curable material solidifies. It can be a material that does not perform when exposed.

In some embodiments, non-curable materials lack polymerizable and/or crosslinkable groups.

Exemplary examples that are suitable for use in this embodiment, meet process conditions, object conditions (e.g., have the hardness of soft body tissues described herein), and are compatible with elastomeric curable formulations. The soft material formulation and its design are given in the Examples section below.

Such soft building formulations are controlled by the type and amount of non-curable material and the amount of non-curable material to provide properties such as printability, compatibility with other curable formulations, and mechanical properties of the printed object. obtained by manipulating the type and amount of curable material. According to some of any of the embodiments described herein, the soft build material formulation includes a curable material and a non-curable material, and the total amount of non-curable material is the soft build material formulation. It ranges from about 10 to about 49%, or from about 10 to about 30%, by weight of the total amount of matter, including any intermediate values and subranges therebetween.

In some embodiments, the total amount of non-curable polymeric material ranges from 20 to 40% by weight or from 25 to 40% by weight of the total amount of the soft building compound, including any intermediate value and Including subranges between.

According to some of any of the embodiments described herein, the soft build material formulation includes a curable material and a non-curable material, a total amount of the curable material and a total amount of the non-curable material. The ratio ranges from 4:1 to 1.1:1, or from 3:1 to 2:1, including any intermediate values and subranges therebetween.

According to some of the embodiments described herein, the total amount of curable material ranges from about 55 to about 70% by weight of the total amount of the soft building compound, which including intermediate values and subranges therebetween.

According to some of any of the embodiments described herein, the curable material includes at least one monofunctional curable material and at least one multifunctional curable material.

According to some of the embodiments described herein, the amount of monofunctional curable material ranges from about 50% to about 89% by weight of the total amount of the soft material formulation, which and intermediate values and subranges therebetween.

According to some of the embodiments described herein, the amount of multifunctional curable material ranges from about 1 to about 10% by weight of the total amount of the soft material formulation, which and intermediate values and subranges therebetween.

According to some of any of the embodiments described herein, the soft building material formulations described herein include monofunctional curable materials, multifunctional curable materials, and non-curable Contains polymeric materials.

In some of the embodiments described herein, the formulation comprises greater than 50% by weight of curable material, i.e., the total amount of monofunctional and multifunctional curable materials is less than or equal to the total amount of the formulation. At least 51% by weight.

As part of any of the embodiments described herein, the total amount of monofunctional and multifunctional curable materials ranges from 51 to 90% or ~89% by weight of the total weight of the formulation; In some embodiments, the range is 55-70% by weight, including any intermediate values and subranges therebetween.

In some of the embodiments described herein, the total amount of monofunctional curable material ranges from 50 to 60%, or from 55 to 60% by weight of the total amount of the formulation, which including any intermediate values and subranges therebetween.

As part of any of the embodiments described herein, the total amount of multifunctional curable material ranges from 3 to 10%, or from 5 to 10%, such as 7% by weight of the total amount of the formulation. , which includes any intermediate values and subranges therebetween.

In some of the embodiments described herein, the total amount of non-curable material is between 10 and 49%, or between 20 and 45%, or between 25 and 40% by weight of the total amount of the formulation. A range, including any intermediate values and subranges therebetween.

In some of the embodiments described herein, the formulation includes:
In any of the respective embodiments described herein in an amount ranging from 50 to 89% by weight of the total weight of the formulation, including any intermediate values and subranges therebetween. Monofunctional curable materials;
In any of the respective embodiments described herein in an amount ranging from 10 to 49% by weight of the total weight of the formulation, including any intermediate values and subranges therebetween. a non-curable polymeric material; and in any of its respective embodiments in an amount ranging from 1 to 10% by weight of the total weight of the formulation, including any intermediate values and subranges therebetween. Multifunctional curable materials described herein.

In some of any of the embodiments described herein, the ratio of the total amount of said monofunctional and said multifunctional curable material to said non-curable polymeric material is from 4:1 to 1.1: 1, or 3:1 to 2:1, including any intermediate values and subranges therebetween.

In part of any of the embodiments described herein, the curable and/or non-curable materials included in the formulation are selected as follows:
(i) said non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, and/or (ii) said non-curable polymeric material has a molecular weight of less than 0°C or less than -10°C or - has a Tg of less than 20°C, and/or (iii) at least 80% by weight of the total amount of said monofunctional curable material and said multifunctional curable material, when cured, is less than 0°C or less than -10°C. or a curable material with a Tg of less than -20°C.

In part of any of the embodiments described herein, the curable and/or non-curable materials included in the formulation are selected as follows:
the non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, the non-curable polymeric material has a Tg of less than 0°C or less than -10°C or less than -20°C, and/ or At least 80% by weight of the total amount of monofunctional and multifunctional curable materials comprises a curable material that, when cured, has a Tg of less than 0°C, or less than -10°C, or less than -20°C.

In some of the embodiments described herein, the curable and/or non-curable materials included in the formulation comprise at least 80% by weight of the total amount of monofunctional and multifunctional curable materials. Selected to include curable materials that, when cured, have a Tg of less than 0°C or less than -10°C or less than -20°C. In some such embodiments, at least 85% or at least 90% or at least 95% or 100% by weight of the total amount of monofunctional and multifunctional curable materials is below 0°C or -10°C when cured. C. or less than -20.degree. C. or less than -20.degree.

In some of the embodiments described herein, the curable and/or non-curable materials included in the formulation comprise at least 80% by weight of the total amount of monofunctional and multifunctional curable materials. Selected to include a curable material that, when cured, has a Tg of less than -20°C.

In part of any of the embodiments described herein, the curable and/or non-curable materials included in the formulation are selected as follows:
The non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, as described herein, and the non-curable polymeric material has a molecular weight of 0 Daltons, as described herein. or less than -10°C or less than -20°C, when at least 80% by weight of the total monofunctional and multifunctional curable material is cured as described herein; It has a Tg of less than -20°C.

In part of any of the embodiments described herein, the curable and/or non-curable materials included in the formulation are selected as follows:
The non-curable polymeric material has a molecular weight of at least 2000 Daltons, as described herein, and the non-curable polymeric material has a Tg of less than -20°C, as described herein. and at least 80% by weight of the total amount of monofunctional and multifunctional curable materials have a temperature of less than 0°C or less than -10°C or less than -20°C when cured as described herein. A curable material having a Tg.

Throughout this specification, "T _g " refers to the glass transition temperature defined as the location of the maximum of the E" curve, and E" is the loss modulus of the material as a function of temperature.

Broadly speaking, as the temperature increases within a temperature range that includes the _Tg temperature, the state of the material, preferably a polymeric material, gradually changes from a glassy state to a rubbery state.

As used herein, a "T _g range" is a temperature range in which the E _" value is at least half of (eg, can be less than) the T g temperature as defined above.

Without wishing to be bound by any particular theory, it is assumed that the state of the polymeric material gradually changes from a glass state to a rubber state within the T _g range as defined above. As used herein, the term " _Tg " refers to any temperature within the _Tg range as defined herein.

As used herein, the term "molecular weight", abbreviated as MW, when referring to polymeric materials, refers to the value known in the industry as Mw, which describes the weight average molecular weight of the polymeric material.

Throughout this specification, whenever the term "wt%" or "weight percentage" or "% wt" is given in the context of an embodiment of a building compound, it refers to the weight of the respective uncured building compound. Means weight percentage of total weight.

Non-curable polymer material:
In some of the embodiments described herein, the non-curable material has a molecular weight of at least 500 or at least 1000 or at least 1500 or at least 2000 Daltons, such as from 500 to 4000 or from 900 to 1400, preferably from 1000 -4000 or 1500-4000, or more preferably 2000-4000 or 2500-4000 or 1500-3500 Daltons, including any intermediate values and subranges therebetween.

In some of any of the embodiments described herein, the non-curable material is less than 0°C or less than -10°C or less than -20°C, such as 0 to -40°C or -20 to -40°C. including any intermediate values and subranges therebetween.

In some of the embodiments described herein, the non-curable material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, as described herein, and As described, it has a Tg of less than 0°C or less than -10°C or less than -20°C.

In some embodiments, the non-curable material has essentially the same properties (e.g., molecular weight and/or Tg) in the build material formulation and in the resulting cured (soft) material upon curing. do.

As used herein, the term "polymeric" with respect to materials includes polymers and copolymers (including block copolymers).

As used herein, the term "block copolymer" describes a copolymer consisting of two or more different regularly or statistically alternating homopolymer blocks that differ in composition or structure. Each homopolymer block in a block copolymer represents one type of polymerized monomer.

Polymeric materials having the above-mentioned MW and/or Tg may include, for example, one or more poly(alkylene glycols) (e.g., poly(ethylene glycol), poly(propylene glycol), and blocks thereof, as defined herein). Polymers or block copolymers, including copolymers (including, for example, pluronic® block copolymers).

In some of any of the embodiments described herein, the non-curable polymeric material comprises polypropylene glycol.

In some embodiments, the non-curable polymeric material is poly(propylene glycol), which in some embodiments is about 2000 Daltons or greater (e.g., 2000, 2200, 2400, 2500, 2600, 2,800, or 3,000 Daltons), including any intermediate values and subranges therebetween.

In some embodiments, the non-curable polymeric material is a block copolymer that includes at least one polypropylene glycol block.

In some embodiments, the non-curable polymeric material is a block copolymer that includes one or more polypropylene glycol blocks and one or more polyethylene glycol blocks. Such block copolymers may be made of, for example, PEG-PPG-PEG or PEG-PPG or PEG-PPG-PEG-PPG or PPG-PEG-PPG, or any other number of blocks in any combination and in any order. can become.

In some of these embodiments, the total amount of poly(ethylene glycol) in the block copolymer is 10% by weight or less.

Thus, for example, in the exemplary block copolymers described above, the length of the PEG blocks is such that the total amount of PEG is 10% by weight or less. As a representative non-limiting example, a PEG-PPG-PEG block copolymer according to these embodiments comprises PEG (wt% A)-PPG (wt% B)-PEG (wt% C), where A+C≦10 and B ≧90, for example A+C=10 and B=90, or A+C=7 and B=93, or A+C=5 and B=95. Similarly, a PPG-PEG-PPG block copolymer is PPG (wt% A)-PEG (wt% B)-PPG (wt% C), where A+C≧90 and B≦10, such as A+C=90 and B=10, or A+C=93 and B=7, or A+C=95 and B=5.

In some of any of the embodiments described herein, the block copolymer has a MW of at least 2000 Daltons.

In some parts of any of the embodiments described herein, for PEG and PPG block copolymers, the number of polypropylene glycol blocks and the number of polyethylene glycol blocks The numerical ratio is at least 1.2:1 or at least 1.5:1 or at least 2:1. An exemplary such block copolymer is PPG-PEG-PPG. Another exemplary block copolymer is PPG-PEG-PPG-PEG-PPG.

Alternatively or additionally, in some of the embodiments described herein for PEG and PPG block copolymers, the total number of polypropylene glycol backbone units and the total number of polyethylene glycol backbone units in the block copolymer The ratio of is at least 2:1 or at least 3:1 or at least 4:1 or at least 5:1 or at least 6:1. Exemplary such block copolymers are PEG-PPG-PEG copolymers or PEG-PPG-PEG-PPG or PEG-PPG-PEG-PPG-PEG with such ratios.

As part of any of the embodiments described herein, the non-curable material has low solubility (e.g., 20% or less or 10% or less) or insolubility in water. characterized by

In the context of these embodiments, the term "water solubility" describes the weight percent of a polymeric material that can be added to 100 grams of water before the solution becomes cloudy (opaque).

In some of the embodiments described herein, the non-curable material has low miscibility (e.g., less than 20% or less than 10% or less) or immiscibility in water. characterized.

Monofunctional polymer materials:
In some of the embodiments described herein, the monofunctional curable material has a Tg of less than -10°C or less than -20°C when cured, such as from 0 to -40°C or -20°C. with a Tg ranging from -40°C, including any intermediate values and subranges therebetween.

As part of any of the embodiments described herein, monofunctional curable materials that can be used in the context of this embodiment can be represented by the following formula:
P-R
where P is a polymerizable group and R is a hydrocarbon as described herein, which is substituted with one or more substituents as described herein. , further optionally interrupted by one or more heteroatoms.

式中、Ｒ_１及びＲ_２の少なくとも一つは、本明細書に規定されるような炭化水素であるか、及び／又はそれを含む。 In some of any of the embodiments described herein, P is a photopolymerizable group, and in some embodiments it is a UV-curable group, so the curable material is It is photopolymerizable or UV curable. In some embodiments, P is an acrylic polymerizable group such as acrylate, methacrylate, acrylamide, or methacrylamide, and such curable groups can be represented collectively by Formula A below:

wherein at least one of R ₁ and R ₂ is and/or comprises a hydrocarbon as defined herein.

The = _CH2 group in Formula I represents a polymerizable group and, according to some embodiments, is a UV-curable group, and thus the monofunctional curable material is a UV-curable material.

In some embodiments, R ₁ is carboxylate, R ₂ is hydrogen, and the compound is a monofunctional acrylate. In some embodiments, R ₁ is carboxylate, R ₂ is methyl, and the compound is a monofunctional methacrylate. Curable materials in which R ₁ is carboxylate and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth)acrylates."

In some of any of these embodiments, the carboxylate group is represented as -C(=O)-OR _a , where R _a is a hydrocarbon as described herein.

In some embodiments, R ₁ is amide, R ₂ is hydrogen, and the compound is a monofunctional acrylamide. In some embodiments, R ₁ is amide, R ₂ is methyl, and the compound is a monofunctional methacrylamide. Curable materials in which R ₁ is amide and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth)acrylamides."

In some of any of these embodiments, the amide group is represented as -C(=O)-NRbRa, where each of Ra and Rb is independently selected from hydrogen and a hydrocarbon, and at least one is , a hydrocarbon as described herein.

(Meth)acrylates and (meth)acrylamides are collectively referred to herein as (meth)acrylic materials.

When one or both of R ₁ and R ₂ include polymeric or oligomeric moieties, the monofunctional curable compounds of Formula A are exemplary polymeric or oligomeric monofunctional curable materials, respectively. Otherwise, it is an exemplary monomeric monofunctional curable material.

Generally, the chemical composition of the hydrocarbon (if present in formula A, R ₁ is of the PR formula, or Ra/Rb) is such that the curable material and the curable material formed therefrom are hydrophilic. , determine whether it is hydrophobic or amphipathic.

As used throughout this specification, the term "affinity" refers to a material or part of a material (e.g., a chemical group in a compound) that serves to temporarily form a bond with a water molecule, generally by hydrogen bonding. Describe physical properties.

Hydrophilic materials dissolve more easily in water than in oil or other hydrophobic solvents. Hydrophilic materials can be determined as having a LogP of less than 0.5, for example when LogP is determined in octanol and aqueous phases.

The hydrophilic material can alternatively or additionally be determined as having a lipophilic/hydrophilic balance (HLB) of at least 10 or at least 12 according to the Davies method.

As used throughout this specification, the term "amphiphilic" refers to hydrophilic, as defined herein for hydrophilic materials, and hydrophobic or lipophilic, as defined herein for hydrophobic materials. Describe the properties of a material that combines both.

Amphiphilic materials generally contain both hydrophilic groups, as defined herein, and hydrophobic groups, as defined herein, in water and in water-immiscible solvents (oils, etc.). ) is substantially soluble in both.

Amphiphilic materials can be determined as having a LogP of 0.8 to 1.2, or about 1, when LogP is determined in octanol and aqueous phases.

Amphiphilic materials can alternatively or additionally be determined as having a lipophilic/hydrophilic balance (HLB) of 3 to 12, or 3 to 9, according to the Davies method.

A hydrophilic material or portion of a material (eg, a chemical group in a compound) is generally one that is charge polarized and capable of hydrogen bonding.

Amphiphilic materials generally contain one or more hydrophilic groups (eg, charge polarized groups) in addition to hydrophobic groups.

Hydrophilic materials or groups and amphiphilic materials generally contain one or more electron-donating heteroatoms that form strong hydrogen bonds with water molecules. Such heteroatoms include, but are not limited to, hydrogen and nitrogen. Preferably, the ratio of the number of carbon atoms to the number of heteroatoms in the hydrophilic material or group is 10:1 or less, such as 8:1, more preferably 7:1, 6:1, 5:1. or 4:1 or less. It should be noted that the hydrophilicity and amphiphilicity of materials and groups also results from the ratio between hydrophobic and hydrophilic moieties in the material or chemical group and does not depend solely on the ratios indicated above. .

Hydrophilic or amphiphilic materials can have one or more hydrophilic groups or moieties. A hydrophilic group is generally a polar group, which contains one or more electron-donating heteroatoms such as hydrogen and nitrogen.

Exemplary hydrophilic groups include, but are not limited to, electron-donating heteroatoms, carboxylates, thiocarboxylates, oxo (=O), linear amides, hydroxy, (C1-4) alkoxy, (C1-4) alcohols, heteroalicyclics (e.g. having a carbon atom to heteroatom ratio as defined herein), cyclic carboxylates such as lactones, cyclic amides such as lactams, carbamates, thiocarbamates, cyanurates, isocyanurates , thiocyanurates, ureas, thioureas, alkylene glycols (e.g. ethylene glycol or propylene glycol), and hydrophilic polymer or oligomeric moieties (these terms are defined below), and combinations thereof (e.g. the hydrophilic groups indicated). (hydrophilic groups containing two or more of the following).

In some embodiments, the hydrophilic group is or includes an electron donating heteroatom, a carboxylate, a heteroalicyclic, an alkylene glycol, and/or a hydrophilic oligomeric moiety.

Amphiphilic moieties or groups generally include one or more hydrophilic groups and one or more hydrophobic groups as described herein, or have a number of carbon atoms and a number of heteroatoms. The ratio can be a heteroatom-containing group or moiety that causes amphipathic properties.

式中、Ｒ_１及びＲ_２は、本明細書に規定された通りであり、Ｒ_１及びＲ_２の少なくとも一方は、明細書に規定された親水性又は両親媒性部分又は基であるか、及び／又はそれらを含む。 The hydrophilic or amphiphilic monofunctional curable material according to some embodiments of the invention can be a hydrophilic acrylate represented by Formula A1 below.

wherein R ₁ and R ₂ are as defined herein, and at least one of R ₁ and R ₂ is a hydrophilic or amphipathic moiety or group as defined herein; and/or containing them.

In some of any of these embodiments, the carboxylate group -C(=O)-ORa comprises Ra that is a hydrophilic or amphipathic moiety or group as defined herein. Exemplary Ra groups in the context of these embodiments include, but are not limited to, heteroalicyclic groups (10:1 or 8:1 or 6:1 or 5:1 or hydroxyl, (C1-4) alkoxy, thiol, alkylene glycol, or hydrophilic or amphiphilic polymer or oligomeric moiety as described herein. including. An exemplary hydrophilic monofunctional acrylate is acryloylmorpholine (ACMO).

Exemplary hydrophilic or amphiphilic oligomeric monofunctional curable materials include, but are not limited to, mono(meth)acrylated urethane oligomer derivatives of polyethylene glycol, mono(meth)acrylated polyol oligomers, monomers with hydrophilic substituents. (meth)acrylated oligomers, mono(meth)acrylated polyethylene glycols (eg, methoxypolyethylene glycol), and monourethane acrylates.

In some embodiments, Ra in Formula A1 is or comprises poly(alkylene glycol) as defined herein.

In some embodiments, Ra in formula A1 includes both an amphipathic group or moiety and a hydrophobic group or moiety as defined herein. Such materials are referred to herein as amphiphilic curable materials containing hydrophobic groups or moieties.

As used throughout this specification, the term "hydrophobic" refers to a material or portion of a material (e.g., a chemical group in a compound or is miscible or soluble in hydrocarbons.

A hydrophobic material or portion thereof (eg, a chemical group or moiety in a compound) is one that is generally not electrically charged or charge polarized and does not have a tendency to form hydrogen bonds.

Hydrophobic materials or groups generally include one or more of alkyl, cycloalkyl, aryl, alkaryl, alkene, alkynyl, etc., which may be unsubstituted or when substituted, alkyl, cycloalkyl, aryl, alkaryl, alkene, alkynyl, etc. The number of carbon atoms and the number of heteroatoms in the hydrophobic material or group, substituted by one or more alkyl, aryl, alkaryl, alkenyl, alkynyl, etc., or other substituents such as electron-donating atom-containing substituents. The ratio of can be at least 10:1, for example 12:1, more preferably 15:1, 16:1, 18:1 or 20:1 or higher.

Hydrophobic materials dissolve more easily in oil than in water or other hydrophilic solvents. Hydrophobic materials can be determined as having a LogP greater than 1, for example when LogP is determined in octanol and aqueous phases.

The hydrophobic material can alternatively or additionally be determined as having a lipophilic/hydrophilic balance (HLB) of less than 9, preferably less than 6, according to the Davies method.

Hydrophobic materials can have one or more hydrophobic groups or moieties that make the material hydrophobic. Such groups are generally non-polar groups or moieties as described above.

In some embodiments, the hydrophobic group or moiety is a hydrocarbon as defined herein of preferably at least 6 atoms, such as an alkylene chain of at least 6 carbon atoms in length. is or contains it. When a hydrocarbon is substituted or interrupted by a heteroatom or a heteroatom-containing group, the ratio of the number of carbon atoms to the number of heteroatoms indicated above applies.

式中、Ｒ_１及びＲ_２は、本明細書に規定された通りであり、Ｒ_１及びＲ_２の少なくとも一方は、明細書に規定された疎水性基又は部分であるか、及び／又はそれらを含む。 The hydrophobic monofunctional curable material according to some embodiments of the invention can be a hydrophobic group acrylate represented by Formula A2 below.

where R ₁ and R ₂ are as defined herein, and at least one of R ₁ and R ₂ is a hydrophobic group or moiety as defined herein, and/or including.

In some of any of these embodiments, the carboxylate group -C(=O)-ORa comprises an Ra that is a hydrophobic group as defined herein. Exemplary hydrophobic monofunctional acrylates are isodecyl acrylate, lauryl acrylate, stearyl acrylate, linolenyl acrylate, bisphenyl acrylate, and the like.

In some embodiments, Ra in formula A2 is or comprises an alkylene chain at least 6 carbon atoms in length, preferably unsubstituted.

In some of any of the embodiments described herein, the monofunctional curable material comprises a hydrophobic monofunctional curable material.

In some of these embodiments, the hydrophobic monofunctional curable material is a hydrophobic monofunctional acrylate, which is also referred to herein as a "monofunctional acrylate type II."

In some of any of the embodiments described herein, the monofunctional curable material comprises a hydrophilic or amphiphilic monofunctional curable material.

In some of any of the embodiments described herein, the monofunctional curable material comprises an amphiphilic monofunctional curable material.

In some of these embodiments, the amphiphilic monofunctional curable material is an amphiphilic monofunctional acrylate free of hydrophobic groups, as described herein; Referred to as "monofunctional acrylate type I".

As part of any of the embodiments described herein, the monofunctional curable material comprises an amphiphilic monofunctional curable material that includes a hydrophobic moiety or group as described herein. , which is also referred to herein as "monofunctional acrylate type II."

In some of any of the embodiments described herein, the monofunctional curable material comprises a combination of an amphiphilic monofunctional curable material and a hydrophobic monofunctional curable material (e.g., monofunctional acrylate type I and combinations of monofunctional acrylates type II).

In some of these embodiments, the weight ratio of amphiphilic monofunctional curable material to hydrophobic monofunctional curable material is from 2:1 to 1:2, preferably from 2:1 to 1:1 or 1. 5:1 to 1:1 or 1.5:1 to 1.1:1, including any intermediate values and subranges therebetween.

In some of any of the embodiments described herein, the monofunctional curable material comprises a hydrophobic monofunctional acrylate, and an amphiphilic monofunctional acrylate containing a hydrophobic group as described herein. combinations of acrylates (eg, combinations of two Type II monofunctional acrylates).

In some of these embodiments, the weight ratio of amphiphilic monofunctional curable material to hydrophobic monofunctional curable material is from 2:1 to 1:2, preferably from 2:1 to 1:1 or 1. 5:1 to 1:1 or 1.5:1 to 1.1:1, including any intermediate values and subranges therebetween.

In some of any of the embodiments described herein, the monofunctional curable material is an amphiphilic monofunctional acrylate (e.g., a Type II monofunctional acrylate containing a hydrophobic group as described herein). (functional acrylate).

In some of the embodiments described herein, the monofunctional curable material, when cured, is less than 0°C, preferably less than -10°C or less than -20°C or lower, e.g. It has a Tg of -20 to -70°C). When the monofunctional curable material includes a combination of two or more materials, at least one of these materials, when cured, has a low Tg as described herein; Typically and preferably all of the materials have such a Tg. Further embodiments of monofunctional curable materials are described in the Examples section below.

Multifunctional Curable Materials As described herein, multifunctional curable materials are monomeric, oligomeric, or polymeric curable materials that include two or more polymerizable groups. Such materials are also referred to herein as crosslinkers.

According to some of any of the embodiments described herein, the multifunctional curable material is a bifunctional curable material. Such materials provide a low degree of crosslinking, thereby providing a low hardness of the cured material.

According to some of any of the embodiments described herein, the multifunctional curable material, when cured, has a Tg of less than -10°C or less than -20°C, such as from -10 to It can have a Tg in the range of -70°C.

式中、Ｒ_３，Ｒ_４及びＲ_５の各々は、独立して水素又はＣ（１－４）アルキルであり；
Ｌ_１は、連結部分、枝分かれユニット又は部分（ｎが１より大きい場合）、又は不存在であり；
Ｌ_２は、連結部分、枝分かれユニット又は部分（ｋが０以外の場合）、又は不存在であり；
Ｌ_３は、連結部分、枝分かれユニット又は部分（ｍが１より大きい場合）、又は不存在であり；
Ｐ_１及びＰ_２の各々は、独立して炭化水素又はオリゴマーもしくはポリマー基又は部分（これらの用語は、本明細書に規定される通りである）、又は不存在であり；
Ｘ_１，Ｘ_２及びＸ_３の各々は、独立してカルボキシレート、アミド、又は不存在であり；
ｎ，ｍ及びｋの各々は、０，１，２，３又は４であり、
但し、ｎ＋ｍ＋ｋは、少なくとも２である。 An exemplary multifunctional curable material according to some embodiments of the invention can be represented by Formula B:

where each of R ₃ , R ₄ and R ₅ is independently hydrogen or C(1-4) alkyl;
L ₁ is a linking moiety, a branching unit or moiety (if n is greater than 1), or absent;
_L2 is a connecting moiety, a branching unit or moiety (if k is other than 0), or absent;
_L3 is a connecting moiety, a branching unit or moiety (if m is greater than 1), or absent;
Each of P ₁ and P ₂ is independently a hydrocarbon or oligomeric or polymeric group or moiety (as these terms are defined herein), or absent;
each of X ₁ , X ₂ and X ₃ is independently carboxylate, amide, or absent;
Each of n, m and k is 0, 1, 2, 3 or 4,
However, n+m+k is at least 2.

Multifunctional curable materials of formula B, where one, two or all of X ₁ , X ₂ and X ₃ (when present) are carboxylates are multifunctional acrylates. When one or more of R ₃ , R ₄ and R ₅ (when present) is methyl, the curable material is a multifunctional methacrylate.

Multifunctional curable materials in which one, two, or all of X ₁ , X ₂ , and X ₃ (when present) are carboxylates can include a combination of acrylate and methacrylate functional moieties.

In some embodiments, the acrylate or methacrylate multifunctional curable material is monomeric, so neither P ₁ nor P ₂ are polymeric or oligomeric moieties. In some of these embodiments, one or both of P ₁ and P ₂ is a hydrophilic or amphiphilic group as described herein, such as an alkylene group or any other hydrophilic or amphipathic group. A medicinal linking group or a short chain (eg, having 1 to 6 carbon atoms), substituted or unsubstituted hydrocarbon moiety as defined herein.

In some embodiments, one or both of P ₁ and P ₂ is a polymeric or oligomeric moiety as defined herein, and _the curable compound is an oligomeric multifunctional curable material, e.g. An oligomeric multifunctional acrylate or methacrylate as described herein for X ₂ and/or X ₃ . If both P ₁ and P ₂ are present, L ₂ can be a linking moiety such as a hydrocarbon including, for example, alkyl, cycloalkyl, aryl and any combination thereof. Exemplary such curable materials include ethoxylated or methoxylated polyethylene glycol diacrylate, and ethoxylated bisphenol A diacrylate.

Other non-limiting examples include polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol-polyethylene glycol urethane diacrylate, acrylated oligourethanes, and partially acrylated polyol oligomers.

In some embodiments, one or more of P ₁ and P ₂ is or includes a poly(alkylene glycol) moiety as defined herein.

Exemplary multifunctional acrylates are described in the Examples section below.

In some of any of the embodiments described herein, the monofunctional curable material and the multifunctional curable material are curable when exposed to the same curing conditions.

In some embodiments, the monofunctional curable material and the multifunctional curable material are both photopolymerizable, and in some embodiments, both are UV curable.

In some embodiments, the monofunctional curable material and the multifunctional curable material are both acrylic compounds, and in some embodiments both (meth)acrylates or both acrylates.

Initiator:
As part of any of the embodiments described herein, the soft building material formulation further comprises one or more agents that promote polymerization of the curable material, referred to herein as an initiator. Ru.

In some of any of the embodiments described herein, a curable material as described herein and an initiator together form a curable system. Such systems can further include inhibitors, as described below.

Compounds/agents that form part of a curable system are not to be considered herein as non-curable materials, even if they are not themselves curable, much less as non-curable materials as described herein. It should be noted that it should not be considered as a polymeric material.

As part of any of the embodiments described herein, a "curable system" refers to one or more curable materials, and optionally the curing of the curable materials, and further optionally the curing of the curable materials. Includes one or more initiators and/or catalysts for initiating one or more conditions (also referred to herein as curing conditions) to induce curing as described herein.

The initiator or initiators are selected according to the curable material selected. Generally, the initiator is further selected according to the polymerization type of the curable material. For example, a free radical initiator is selected to initiate free radical polymerization (such as in the case of acrylic curable materials), a cationic initiator is selected to initiate cationic polymerization, and so on. Additionally, photoinitiators are used when one or more of the curable materials are photopolymerizable.

In some of any of the embodiments described herein, the curable system is a photocurable system and the initiator is a photoinitiator.

In some embodiments, the curable system includes an acrylic compound and the photoinitiator is a free radical photoinitiator.

A free radical photoinitiator can be any compound that generates free radicals upon exposure to radiation, such as ultraviolet or visible radiation, thereby initiating a polymerization reaction. Non-limiting examples of suitable photoinitiators include benzophenones (aromatic ketones) such as benzophenone, methylbenzophenone, Michler's ketone and xanthone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TMPO), 2,4,6- Acyl phosphine oxide type photoinitiators such as trimethylbenzoylethoxyphenylphosphine oxide (TEPO), and bisacylphosphine oxide (BAPO); benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, and benzoin isopropyl ether; include. Examples of photoinitiators are alpha-aminoketones and bisacylphosphine oxide (BAPO). Further examples include the Irgacure® family of photoinitiators.

Free radical photoinitiators can be used alone or in combination with coinitiators. Coinitiators are used with initiators that require a second molecule to generate radicals that are active in photocurable free radical systems. Benzophenone is an example of a photoinitiator that requires a second molecule, such as an amine, to generate free radicals. After absorbing radiation, benzophenone reacts with tertiary amines by hydrogen abstraction to generate alpha-amino radicals that initiate polymerization of acrylates. Non-limiting examples of coinitiators are alkanolamines such as triethylamine, methyldiethanolamine, and triethanolamine.

As part of any of the embodiments described herein, the build material formulation includes a free radical curable system and is further configured to prevent or slow polymerization and/or curing prior to exposure to curing conditions. Contains radical inhibitors.

In some of the embodiments described herein, the curable system is polymerizable or cured by cationic polymerization and is referred to herein as a cationically polymerizable or cationically curable system. .

In some embodiments, the cationically polymerizable material is photopolymerizable or curable by exposure to radiation. Systems containing such materials can be referred to as photopolymerizable cationic systems or photoactivatable cationic systems.

In some embodiments, the cationically curable system further includes a cationic initiator, which generates cations to initiate polymerization and/or curing.

In some embodiments, the initiator is a cationic photoinitiator, which generates cations upon exposure to radiation.

Suitable cationic photoinitiators include, for example, compounds that form aprotic or Brønsted acids upon exposure to sufficient ultraviolet and/or visible light to initiate polymerization. The photoinitiator used can be a single compound, a mixture of two or more active compounds or a combination of two or more different compounds, ie coinitiators. Non-limiting examples of suitable cationic photoinitiators include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triarylselenonium salts, and the like. An exemplary cationic photoinitiator is a mixture of triarylsulfonium hexafluoroantimonate salts.

Non-limiting examples of suitable cationic photoinitiators include P-(octyloxyphenyl)phenyliodonium hexafluoroantimonate (UVACURE 1600 from Cytec Company (USA)), Irgacure 250 available from Ciba Specialty Chemicals (Switzerland) or Iodonium (4-methylphenyl)(4-(2-methylpropyl)phenyl)-hexafluorophosphate known as Irgacure 270, mixed arylsulfonium hexafluoroantimonate known as UVI 6976 and 6992 available from Lambson Fine Chemicals (UK) salt, diaryliodonium hexafluoroantimonate known as PC2506 available from Polyset Company (USA), (tolylcumyl)iodonium tetrakis(penta fluorophenyl)borate, iodonium bis(4-dodecylphenyl)-(OC-6-11)-hexafluoroantimonate known as Tego PC1466 from Evonik Industries AG (Germany).

In some of the embodiments described herein, the amount of initiator (e.g., free radical photoinitiator) ranges from 1 to 5% or 1 to 3% by weight, which and intermediate values and subranges therebetween. In an exemplary embodiment, two or more initiators (eg, photoinitiators) are used, each in an amount ranging from 1 to 3% by weight.

Additional ingredients:
According to some of any of the embodiments described herein, the soft building material includes additional non-curable ingredients, such as inhibitors, surfactants, dispersants, colorants, and stabilizers. further including. Commonly used surfactants, dispersants, colorants, and stabilizers are contemplated. Exemplary concentrations of each component (if present) are from about 0.01% to about 1%, or from about 0.01% to about 0.5% by weight of the total weight of the formulation containing it. , or in the range of about 0.01% to about 0.1% by weight. Exemplary components are described below.

In some of any of the embodiments described herein, the formulation includes a cure inhibitor, ie, an agent that inhibits or reduces the amount of cure in the absence of cure conditions. In some embodiments, the inhibitor is a free radical polymerization inhibitor. In some embodiments, the amount of inhibitor (e.g., free radical inhibitor) ranges from 0.01 to 2, or 1 to 2, or 0.05 to 0.15%, or 0.1% by weight. , which includes any intermediate values and subranges therebetween. However, it depends on the type of inhibitor used. Commonly used inhibitors, such as radical inhibitors, come into consideration.

In exemplary embodiments, the free radical inhibitor, such as NPAL, or equivalent thereof, is present in a range of 0.01 to 1, or 0.05 to 2, or 0.05 to 0.15% by weight, or 0. Used in an amount of .1% by weight.

In an alternative embodiment, free radical inhibitors lacking nitro or nitroso groups are used. Exemplary such inhibitors are from the Genorad™ family (eg, Genorad 18).

In exemplary embodiments, such free radical inhibitors are used in an amount of 0.1 to 3, or 0.1 to 2, or 0.5 to 2, or 1 to 1.5% by weight; including any intermediate values and subranges therebetween.

In an exemplary embodiment, the soft building material formulation includes a surfactant. Exemplary surfactants are those sold as BYK surfactants. In some embodiments, the surfactant is a curable material that is preferably curable when exposed to the same curing conditions as the curable material in the formulation. In some embodiments, the surfactant is a UV-curable surfactant, and in some embodiments, the surfactant is a UV-curable BYK surfactant (e.g., BYK UV-3150 or BYK UV- 3500).
In some embodiments, the amount of surfactant in the formulation ranges from 0.1 to 1% by weight, as described herein.

Exemplary soft modeling compounds:
In part of any of the embodiments described herein, the soft build material formulation comprises a non-curable polymeric material as described herein and a monofunctional acrylate (e.g., amphiphilic and a combination of hydrophobic monofunctional acrylates), a free radical photoinitiator, and optionally a free radical inhibitor.

In some embodiments, the formulation further comprises one or more additional ingredients as described herein.

In some embodiments, the formulation includes, for example, a red, fleshy color to the formulation, or a skin or skin pigment color to the formulation and to objects or parts made therefrom. It further includes a colorant as described herein. Exemplary fleshy colors suitable for use with acrylic materials include, but are not limited to, those available from Prosthetic Research Specialists, Inc. as the "Flesh color system." and those manufactured by Kingsley Mfg. Co. Including those sold by.

In some embodiments, the concentration of coloring depends on the intended use of the formulation and the desired visual properties of the object, and may vary from 0.01 to 5, or from 0.01 to 1, or from 0.1 to 1. 1% by weight, including any intermediate values and subranges therebetween.

In part of any of the embodiments described herein, the soft building material formulation includes:
a monofunctional amphiphilic acrylate described herein in any of the respective embodiments in an amount of 25-35% by weight;
a monofunctional hydrophobic acrylate described herein in any of the respective embodiments in an amount of 25-30% by weight;
A monofunctional acrylate as described herein in any of its respective embodiments in an amount of 5 to 10% by weight; and a monofunctional acrylate described herein in any of its respective embodiments in an amount of 30 to 35% by weight. A non-curable polymeric material having a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons and a Tg of less than 0°C or less than -10°C or less than -20°C as described.

In some of these embodiments, the non-curable polymeric material comprises polypropylene glycol and/or a block copolymer comprising at least one polypropylene glycol block, each of which is described herein in any of its respective embodiments. As described, it has a molecular weight of at least 2000 Daltons.

In some of these embodiments, the monofunctional acrylate is a difunctional acrylate, and in some embodiments it is a urethane diacrylate.

In some of these embodiments, the monofunctional amphiphilic acrylate includes a hydrocarbon chain of at least 6 carbon atoms and at least 2 alkylene glycol groups.

In some of these embodiments, the monofunctional hydrophobic acrylate includes a hydrocarbon chain of at least 8 carbon atoms.

An exemplary formulation is provided in Example 2 in the Examples section below.

According to some of any of the embodiments described herein, the uncured build material comprises two or more soft building material formulations as described herein, each of which , comprising different combinations of curable and non-curable materials according to the present embodiments, each optionally having a different Shore A hardness value in the range of 1 to 10 and/or in the range of 0 to 40 when cured. with different Shore OO hardness values.

In some embodiments, such two or more build material formulations represent a formulation system of soft building compounds.

Elastomer curable formulation:
Throughout this specification, the term "elastomeric curable formulation" is also referred to herein as "elastomeric building material formulation,""elastomeric building formulation," or simply "elastomeric formulation," and the curing When used, describes a compound that has the properties of a rubber or rubber-like material, which is also referred to herein and in the industry as an elastomer.

Elastomers or rubbers are flexible materials characterized by a low Tg below room temperature, preferably below 10°C, below 0°C, even below -10°C.

Exemplary such formulations are those sold as the Tango(TM), Tango+(TM), and Agilus(TM) families.

Exemplary such formulations are described in PCT/IL2017/050604, which is incorporated by reference as if fully set forth herein.

Whenever "Agilus" or "Agilus formulation" is referred to, it means a formulation of the Agilus family (e.g. the formulation described in WO 2017/208238), such as Agilus 30. do.

According to some of any of the embodiments described herein, the elastomeric curable building compound includes at least one elastomeric curable material.

The expression "elastomeric curable material" describes a curable material as defined herein which, when exposed to curing energy, provides a cured material with the properties of an elastomer (rubber or rubber-like material). do.

Elastomeric curable materials generally include one or more polymerizable moieties that undergo polymerization upon exposure to suitable curing conditions (e.g., curing energy) coupled to a moiety that imparts elasticity to the polymerized and/or crosslinked material. (curable) groups. Such moieties generally include alkyls, alkylene chains, hydrocarbons, alkylene glycol groups or chains (e.g., oligo- or poly(alkylene glycols)), as defined herein; , urethane, oligourethane, or polyurethane moieties, and the like, as well as combinations of any of the foregoing, referred to herein as "elastomeric moieties."

Elastomeric curable materials can be monofunctional or multifunctional materials, or combinations thereof.

式Ｉ中のＲ_１及びＲ_２の少なくとも一つは、本明細書に規定されるようなエラストマー部分であるか、及び／又はそれを含む。 Elastomeric monofunctional curable materials according to some embodiments of the invention can be vinyl-containing compounds represented by Formula I below:

At least one of R ₁ and R ₂ in Formula I is and/or comprises an elastomeric moiety as defined herein.

The = _CH2 group in Formula I represents a polymerizable group and, according to some embodiments, is a UV-curable group, and thus the elastomeric curable material is a UV-curable material.

For example, R ₁ in Formula I is or includes an elastomeric moiety as defined herein, and R ₂ is, for example, as long as it does not interfere with the elastomeric properties of the cured material. hydrogen, C(1-4) alkyl, C(1-4) alkoxy, or any other substituent.

In some embodiments, R ₁ in Formula I is a carboxylate as described herein, R ₂ is hydrogen, and the compound is a monofunctional acrylate monomer. In some embodiments, R ₁ in Formula I is a carboxylate as described herein, R ₂ is methyl, and the compound is a monofunctional methacrylate monomer. Curable materials in which R ₁ is carboxylate and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth)acrylates."

In some of any of these embodiments, the carboxylate group is represented by -C(=O)-OR _c and R _c is an elastomeric moiety as described herein.

In some embodiments, R ₁ in Formula I is amide as described herein, R ₂ is hydrogen, and the compound is a monofunctional acrylamide monomer. In some embodiments, R ₁ in Formula I is amide as described herein, R ₂ is methyl, and the compound is a monofunctional methacrylamide monomer. Curable materials in which R ₁ is amide and R ₂ is hydrogen or methyl are collectively referred to herein as "(meth)acrylamides."

(Meth)acrylates and (meth)acrylamides are collectively referred to herein as (meth)acrylic materials.

In some embodiments, the amide is represented by -C(=O)-NRdRe, where Rd and Re are selected from hydrogen and an elastomer moiety, and at least one is as defined herein. This is the elastomer part. When one or both of R ₁ and R ₂ in Formula I includes a polymeric or oligomeric moiety, the monofunctional curable compounds of Formula I are exemplary polymeric or oligomeric monofunctional curable materials. Otherwise, it is an exemplary monomeric monofunctional curable material.

In multifunctional elastomeric materials, two or more polymerizable groups are linked together by an elastomeric moiety as described herein.

In some embodiments, the multifunctional elastomeric material can be represented by Formula I as described herein, where R ₁ is a polymerizable group as described herein. Contains an elastomeric material terminated by.

式中、Ｅは、本明細書に記載されるようなエラストマー連結部分であり、Ｒ’_２は、式Ｉ中のＲ_２に対して本明細書に規定されたようなものである。 For example, a difunctional elastomeric curable material can be represented by the following formula I ^* :

where E is an elastomeric linking moiety as described herein and _R'2 is as defined herein for _R2 in Formula I.

式中、Ｅは、本明細書に記載されるようなエラストマー連結部分であり、Ｒ’_２及びＲ”_２は、各々独立して、式Ｉ中のＲ_２に対して本明細書に規定されたようなものである。 In another example, the trifunctional elastomeric curable material can be represented by Formula II below:

where E is an elastomeric linking moiety as described herein, and R' ₂ and R'' ₂ are each independently defined herein for R ₂ in Formula I. It's like that.

式中、Ｒ_２及びＲ’_２は、本明細書に規定されるようなものであり、
Ｂは、（Ｘ_１の性質に依存して）本明細書に規定されるような二官能又は三官能枝分かれ単位であり、
Ｘ_２及びＸ_３は、各々独立して、存在しないか、本明細書に記載されるようなエラストマー部分であるか、又はアルキル、炭化水素、アルキレン鎖、シクロアルキル、アリール、アルキレングリコール、ウレタン部分、及びそれらのいずれかの組み合わせから選択され、
Ｘ_１は、存在しないか、又はアルキル、炭化水素、アルキレン鎖、シクロアルキル、アリール、アルキレングリコール、ウレタン部分、及びエラストマー部分（各々は、任意選択的にメタ（アクリレート）部分（Ｏ－Ｃ（＝Ｏ）ＣＲ”_２＝ＣＨ_２）によって置換（例えば終了）される）、及びそれらのいずれかの組み合わせから選択され、又はＸ_１は、以下のものである：

式中、曲線は、結合点を表わし、
Ｂ’は、枝分かれ単位であり、それは、Ｂと同じであるか又はＢとは異なり、
Ｘ’_２及びＸ’_３は、各々独立して、Ｘ_２及びＸ_３に対して本明細書に規定されるようなものであり、
Ｒ”_２及びＲ”’_２は、Ｒ_２及びＲ’_２に対して本明細書に規定されるようなものであり、
但し、Ｘ_１、Ｘ_２、及びＸ_３の少なくとも一つは、本明細書に記載されるようなエラストマー部分であるか、又はそれを含む。 In some embodiments, multifunctional (e.g., difunctional, trifunctional, or more functional) elastomeric curable materials can be collectively represented by Formula III:

where R ₂ and R′ ₂ are as defined herein;
B is a difunctional or trifunctional branching unit as defined herein (depending on the nature of X ₁ );
X ₂ and X ₃ are each independently absent, an elastomer moiety as described herein, or an alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane moiety , and any combination thereof,
X ₁ is either absent or alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane moiety, and elastomeric moiety (each optionally a meth(acrylate) moiety (OC(= O) substituted (e.g., terminated) by CR'' ₂ =CH ₂ ), and any combination thereof, or X ₁ is:

In the formula, the curve represents the connection point,
B' is a branching unit, which is the same as or different from B;
X' ₂ and X' ₃ are each independently as defined herein for X ₂ and X ₃ ;
R'' ₂ and R''' ₂ are as defined herein for R ₂ and R'₂;
provided that at least one of X ₁ , X ₂ , and X ₃ is or includes an elastomer moiety as described herein.

The term "branching unit" as used herein describes a linking moiety of multiple radicals, preferably aliphatic or cycloaliphatic. By "multiple radicals" is meant that the linking moiety has more than one point of attachment, so that it links between two or more atoms and/or groups or moieties.

That is, when a branching unit is attached to a single location, group, or atom of a substance, it creates two or more functional groups that are attached to this single location, group, or atom, thus forming a single It is a chemical moiety that "branches" a function into two or more functions.

In some embodiments, branching units are derived from chemical moieties with two, three, or more functional groups. In some embodiments, the branching unit is a branched alkyl or a branched linking moiety as described herein.

Multifunctional elastomeric curable materials with four or more polymerizable groups are also contemplated, with structures similar to those given in formula III (but containing branching units B with, for example, greater branching, or (including _an (meth)acrylate moiety).

In some embodiments, the elastomeric moiety (e.g., the moiety designated as R _c in Formula I or E in Formulas I ^* , II, and III) is or includes an alkyl, which is linear or branched, preferably 3 or more or 4 or more carbon atoms; preferably 3 or more or 4 or more carbon atoms in length an alkylene chain of atoms; an alkylene glycol as defined herein, an oligo(alkylene glycol), or a poly(alkylene glycol) as defined herein preferably of a length of four or more atoms; ), preferably 4 or more carbon atoms in length, urethanes, oligourethanes, or polyurethanes as defined herein, and combinations thereof.

In some of any of the embodiments described herein, the elastomeric curable material is a (meth)acrylic curable material as described herein, and in some embodiments it is , an acrylate.

In some of any of the embodiments described herein, the elastomeric curable material is or includes a monofunctional elastomeric curable material, and in some embodiments, the elastomeric curable material is a monofunctional elastomeric curable material. is represented by formula I, where R ₁ is -C(=O)-OR _a and R _a is an alkylene chain (e.g. four or more), as defined herein. preferably 6 or more, preferably 8 or more carbon atoms in length), or a poly(alkylene glycol) chain.

In some embodiments, the elastomeric curable material is or includes a multifunctional elastomeric curable material, and in some embodiments, the multifunctional elastomeric curable material is represented by formula I ^* , where E is an alkylene chain (e.g., 4 or more, or 6 or more carbon atoms in length), and/or a poly(alkylene glycol) chain, as defined herein. It is.

In some embodiments, the elastomeric curable material is or comprises a multifunctional elastomeric curable material, and in some embodiments, the multifunctional elastomeric curable material is represented by Formula II, wherein E is a branched alkyl (eg, 3 or more, or 4 or more, or 5 or more carbon atoms in length).

In some of the embodiments described herein, the elastomeric curable material is, for example, an elastomeric acrylate or methacrylate (also referred to as an acrylic or methacrylic elastomer) of formula I, I ^* , II or III. In some embodiments, the acrylate or methacrylate is selected such that, when cured, the polymeric material has a T _g of less than 0° C. or less than −10° C.

Exemplary elastomeric acrylate and methacrylate curable materials include 2-propanoic acid, 2-[[(butylamino)carbonyl]oxy]ethyl ester (an exemplary urethane acrylate), and the tradenames SR335 (lauryl acrylate) and SR395 ( isodecyl acrylate) (by Sartomer). Other examples include trade names SR350D (trifunctional trimethylolpropane trimethacrylate (TMPTMA)), SR256 (2-(2-ethoxyethoxy)ethyl acrylate), SR252 (polyethylene glycol (600) dimethacrylate), SR561 (alkoxylated Hexanediol diacrylate) (by Sartomer).

It should be noted that other acrylic materials are also conceivable, for example with one or more acrylamide groups instead of one or more acrylate or methacrylate groups.

As part of any of the embodiments described herein, the elastomeric curable material includes one or more monofunctional elastomeric curable materials ( (e.g., monofunctional elastomeric acrylates, such as those of formula I) and one or more polyfunctional (e.g., difunctional) elastomeric curable materials (e.g., difunctional elastomeric acrylates, such as those of formula I ^* , II, or III). .

In some of the embodiments described herein, the total amount of elastomeric curable material is at least 40%, or at least 50% of the total amount of the elastomeric building material formulation as described herein. %, or at least 60%, and can be up to 70%, or even up to 80%.

In some of any of the embodiments described herein, the elastomeric curable building compound further comprises silica particles.

In some of any of the embodiments described herein, the silica particles have an average particle size of less than 1 micron, ie, the silica particles are submicron particles. In some embodiments, the silica particles have an average particle size ranging from 0.1 nm to 900 nm, or from 0.1 nm to 700 nm, or from 1 nm to 700 nm, or from 1 nm to 500 nm, or from 1 nm to 200 nm, and between Nanosized particles or nanoparticles, including any intermediate values and subranges of.

In some embodiments, at least a portion of such particles are capable of agglomerating upon introduction into the formulation. In some of these embodiments, the aggregates have an average size of 3 microns or less, or 1.5 microns or less.

Any commercially available formulation of submicron silica particles can be used in the context of this embodiment, including fumed silica, colloidal silica, precipitated silica, layered silica (e.g. montmorillonite), and Including aerosol-assisted self-assembly of silica particles.

Silica particles can be such that they have a hydrophobic or hydrophilic surface. The hydrophobicity or hydrophilicity of the surface of a particle is determined by the nature of the surface groups on the particle.

When the silica is untreated, ie, composed essentially of Si and O atoms, the particles generally comprise silanol (Si-OH) surface groups and are therefore hydrophilic. Untreated (uncoated) colloidal silica, fumed silica, precipitated silica, and layered silica all have hydrophilic surfaces and are considered hydrophilic silica.

The layered silica can be treated to have quaternary ammonium and/or long chain hydrocarbons terminated by ammonium as surface groups, the nature of the surface being determined by the length of the hydrocarbon chains. Hydrophobic silica is a form of silica in which hydrophobic groups are attached to the surface of the particles, also referred to as treated silica or functionalized silica (silica reacted with hydrophobic groups).

As defined herein, alkyl, preferably 2 or more carbon atoms in length, preferably 4 or more carbon atoms in length, or 6 or more carbon atoms in length Silica particles having a large degree of hydrophobic surface groups such as, but not limited to, alkyl, cycloalkyl, aryl, and other hydrocarbons, or hydrophobic polymers (e.g., polydimethylsiloxane) are particles of hydrophobic silica. .

Silica particles as described herein can therefore be untreated (non-functionalized) and are therefore hydrophilic particles.

Alternatively, silica particles as described herein can be treated or functionalized by reacting to form bonds with moieties on their surface.

When the moiety is a hydrophilic moiety, the functionalized silica particles are hydrophilic.

Silica particles with hydrophilic surface groups such as, but not limited to, hydroxy, amine, ammonium, carboxy, silanol, oxo, and the like are particles of hydrophilic silica.

When the moiety is a hydrophobic moiety as described herein, the functionalized silica particles are hydrophobic.

In some of any of the embodiments described herein, at least some or all of the silica particles have a hydrophilic surface (i.e., hydrophilic silica particles of untreated silica, such as colloidal silica). ).

In some of any of the embodiments described herein, at least some or all of the silica particles have a hydrophobic surface (ie, are hydrophobic silica particles).

In some embodiments, the hydrophobic silica particles are functionalized silica particles, ie, particles of silica that have been treated with one or more hydrophobic moieties.

In some of any of the embodiments described herein, at least some or all of the silica particles are hydrophobic silica particles functionalized with curable functional groups (with curable groups on the surface). particles).

The curable functional group can be any polymerizable group as described herein. In some embodiments, the curable functional group is polymerizable by the same polymerization reaction and/or when exposed to the same curing conditions as the curable monomer in the formulation. In some embodiments, the curable group is a (meth)acrylic (acrylic or methacrylic) group, as defined herein.

Hydrophilic and hydrophobic, functionalized and untreated silica particles as described herein can be commercially available materials or prepared using methods well known in the art. can be manufactured.

"At least a portion" as used in the context of these embodiments means at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least It means 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%.

The silica particles can also be a mixture of two or more types of silica particles, such as a mixture of two or more of any of the silica particles described herein.

As part of any of the embodiments described herein, the amount of silica particles in the build material formulation is from about 1% to about 20% by weight of the total weight of the build material formulation, or It ranges from about 1% to about 15% by weight, or from about 1% to about 10% by weight.

As part of any of the embodiments described herein, the amount of silica particles in a formulation system as described herein ranges from about 1% to about 1% by weight of the total weight of the formulation system. 20% by weight, or from about 1% to about 15%, or from about 1% to about 10%.

In some embodiments, the formulation system includes one type of formulation. In some embodiments, the formulation system includes more than one formulation, and the silica particles are included in one, two, or all of the formulations.

The amount of silica particles can be manipulated as desired to control the mechanical properties of the cured building material and/or the object or portion thereof containing it. For example, increasing the amount of silica particles can increase the modulus of the cured building material and/or the object or portion thereof containing it.

In some of the embodiments described herein, the amount of silica particles is such that the weight ratio of elastomeric curable material to silica particles in the one or more building material formulations is from about 50:1 to from about 4:1, or from about 30:1 to about 4:1, or from about 20:1 to about 2:1, including any intermediate values and subranges therebetween. be.

According to some of any of the embodiments described herein, the elastomeric building material formulation further comprises one or more additional curable materials.

The additional curable material can be a monofunctional curable material, a multifunctional curable material, or a mixture thereof, and each material can be a monomer, oligomer, or polymer, or a combination thereof.

Preferably, although not necessarily, the additional curable material is polymerizable when exposed to the same curing energy that the curable elastomeric material is polymerizable, for example when exposed to light radiation (eg UV radiation).

In some embodiments, the additional curable material has a T _g that, when cured, the polymerized material is greater than the T _g of the elastomeric material, such as a T _g greater than 0° C., or greater than 5° C. T _g , or such that it has a T _g greater than 10°C.

In some embodiments, the additional curable material is, for example, a non-elastomeric curable material that, when cured, has a different modulus and/or T _g than that exhibiting the elastomeric material.

In some embodiments, the additional curable material is a monofunctional acrylate or methacrylate ((meth)acrylate). Non-limiting examples include isobornyl acrylate (IBOA), isobornyl methacrylate, acryloyl morpholine (ACMO), phenoxyethyl acrylate sold by Sartomer Company (USA) under the trade name SR-339, trade name CN131B and any other acrylates and methacrylates that can be used in AM methodologies.

In some embodiments, the additional curable material is a multifunctional acrylate or methacrylate ((meth)acrylate). Non-limiting examples of multifunctional (meth)acrylates include propoxylated (2) neopentyl glycol diacrylate, ditrimethylolpropane tetraacrylate (DiTMPTTA), sold by Sartomer Company (USA) under the trade name SR-9003. ), pentaerythritol tetraacrylate (TETTA), and dipentaerythritol pentaacrylate (DiPEP), and aliphatic urethane diacrylates, such as sold as Ebecryl 230. Non-limiting examples of polyfunctional (meth)acrylate oligomers include ethoxylated or methoxylated polyethylene glycol diacrylate or dimethacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol-polyethylene glycol urethane diacrylate, partially acrylated polyols. oligomers, including polyester-based urethane diacrylates such as those sold as CNN91.

Any other curable material, preferably a curable material, having a T _g as defined herein is contemplated as an additional curable material.

In some of any of the embodiments described herein, the elastomeric building material formulation further comprises an initiator to initiate polymerization of the curable material.

Photoinitiators can be used in these embodiments when all curable materials (elastomer and additions, if present) are photopolymerizable.

When all curable materials (elastomer and additions, if present) are acrylic or otherwise photopolymerizable by free radical polymerization, as described herein Free radical photoinitiators can be used in these embodiments.

The concentration of the photoinitiator can range from about 0.1% to about 0.5% by weight, or from about 1% to about 5% by weight in curable elastomer formulations containing it; , including any intermediate values and subranges therebetween.

According to some of any of the embodiments described herein, the elastomeric build material formulation includes one or more additional additives, as described herein for soft build material formulations. The composition further includes non-curable materials such as one or more colorants, dispersants, surfactants, stabilizers, and inhibitors.

In some of any of the embodiments described herein, the elastomeric curable material is a UV curable material, and in some embodiments it is an elastomeric (meth)acrylate, e.g., an elastomeric acrylate. .

In some of any of the embodiments described herein, an additional curable component is included in the elastomeric building material formulation, and in some embodiments this component is UV curable acrylate or It is methacrylate.

In some of any of the embodiments described herein, the silica particles are (meth)acrylate functionalized silica particles.

In some of any of the embodiments described herein, the elastomeric building material formulation comprises one or more monofunctional elastomeric acrylates, one or more multifunctional elastomeric acrylates, one or more monofunctional acrylates or methacrylates, and one or more polyfunctional acrylates or methacrylates.

In some of these embodiments, the elastomeric building material formulation further comprises one or more photoinitiators, such as from the Irgacure family.

In some of any of the embodiments described herein, all curable materials and silica particles are included in a single material formulation.

In some of any of the embodiments described herein, the elastomeric building formulation comprises two or more building material formulations, and an elastomeric curable formulation as described herein. to form an elastomer formulation system comprising:

In some of these embodiments, one type of build material formulation (e.g., first formulation or part A) includes an elastomeric curable material (e.g., elastomeric acrylate) and another type of build material formulation (e.g., elastomeric acrylate) For example, the second formulation or part B) contains additional curable materials.

Alternatively, each of the two build material formulations includes an elastomeric curable material, and one of the formulations further includes an additional curable material.

Still alternatively, each of the two building material formulations in the elastomeric formulation system includes an elastomer curable, but the elastomeric material is different in each formulation. For example, one type of formulation includes a monofunctional elastomeric curable material, and another type of formulation includes a multifunctional elastomeric material. Alternatively, one type of formulation comprises a mixture of monofunctional and multifunctional elastomeric curable materials in a ratio W, and another type of formulation comprises a mixture of monofunctional and multifunctional elastomeric curable materials in a ratio Q However, W and Q are different.

Whenever each of the build material formulations includes an elastomeric material described herein, one or more build material formulations in the elastomeric formulation system can further include additional curable materials. can. In an exemplary embodiment, one type of formulation includes additional monofunctional materials and another type of formulation includes additional materials that are multifunctional. In a further exemplary embodiment, one type of formulation includes an oligomeric curable material and another type of formulation includes a monomeric curable material.

Any combination of elastomeric curable materials and additional curable materials as described herein are contemplated for inclusion in two or more building material formulations to form an elastomeric formulation system. Selection of the composition of the building material formulation and the printing mode allows for the fabrication of objects with a variety of properties in a controllable manner, as described in further detail below.

In some embodiments, the one or more building material formulations in the elastomeric formulation system provide a rubber-like material such that the ratio of elastomeric curable material to additional curable material is as described herein. selected as follows.

In some embodiments, silica particles, one or more photoinitiators, and optionally other ingredients are included in one or both building material formulations.

In an exemplary build material formulation according to some of the embodiments described herein, all curable materials are (meth)acrylates.

In any of the exemplary building material formulations described herein, the concentration of photoinitiator is from about 1% to about 5% by weight of the total weight of the formulation or formulation system containing it; or about 2% to about 5%, or about 3% to about 5%, or about 3% to about 4% (e.g., 3, 3.1, 3.2, 3.25, 3 .3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.85, 3.9% by weight, including any intermediate values therebetween).

In any of the exemplary build material formulations described herein, the concentration of inhibitor is from 0% to about 2% by weight of the total weight of the formulation or formulation system containing it, or 0% to about 2% by weight of the total weight of the formulation or formulation system containing it. % by weight to about 1% by weight, such as 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or about 1% by weight, including any intermediate values therebetween.

In any of the exemplary building material formulations described herein, the concentration of surfactant is from 0% to about 1% by weight of the total weight of the formulation or formulation system containing it. , for example 0, 0.01, 0.05, 0.1, 0.5 or about 1% by weight, including any intermediate values therebetween.

In any of the exemplary build material formulations described herein, the concentration of dispersant is from 0% to about 2% by weight of the total weight of the formulation or formulation system containing it; For example, 0, 0.1, 0.5, 0.7, 1, 1.2, 1.3, 1.35, 1.4, 1.5, 1.7, 1.8 or about 2% by weight. , and it includes any intermediate values between them.

In exemplary build material formulations according to some of the embodiments described herein, the total concentration of elastomeric curable material is from about 30% to about 90%, or about 40% by weight. and about 90% by weight, or from about 40% to about 85% by weight.

"Total concentration" throughout this specification refers to the total weight of all of the elastomeric building material formulation(s) or elastomeric formulation system as described herein.

In some embodiments, the elastomeric curable materials include monofunctional elastomeric curable materials and multifunctional elastomeric curable materials.

In some embodiments, the total concentration of monofunctional elastomeric curable material ranges from about 20% to about 70% by weight, or from about 30% to about 50% by weight; Also includes intermediate values and subranges. In exemplary embodiments, the total concentration of monofunctional elastomeric curable material is from about 50% to about 70%, or from about 55% to about 65%, or from about 55% to about 60% (by weight). 58% by weight), including any intermediate values and subranges therebetween. In exemplary embodiments, the total concentration of monofunctional elastomeric curable material is from about 30% to about 50%, or from about 35% to about 50%, or from about 40% to about 45% (by weight). 42% by weight), including any intermediate values and subranges therebetween.

In some embodiments, the total concentration of multifunctional elastomeric curable material ranges from about 10% to about 30% by weight. In exemplary embodiments, the total concentration of monofunctional elastomeric curable material ranges from about 10% to about 20%, or from about 10% to about 15% (eg, 12%) by weight. In exemplary embodiments, the total concentration of monofunctional elastomeric curable material is from about 10% to about 30%, or from about 10% to about 20%, or from about 15% to about 20% (by weight). For example, 16% by weight).

In exemplary build material formulations according to some of the embodiments described herein, the total concentration of additional curable material is about 10% to about 40% by weight, or about 15% by weight. % to about 35% by weight, including any intermediate values and subranges therebetween.

In some embodiments, the additional curable material comprises a monofunctional curable material.

In some embodiments, the total concentration of monofunctional additional curable material ranges from about 15% to about 25%, or from about 20% to about 25% (e.g., 21%) by weight. , including any intermediate values and subranges therebetween. In exemplary embodiments, the concentration of monofunctional elastomeric curable material ranges from about 20% to about 30%, or from about 25% to about 30% (eg, 28%) by weight; including any intermediate values and subranges therebetween.

In an exemplary elastomeric building material formulation or formulation system according to a portion of any of the embodiments described herein, the elastomeric curable materials include monofunctional elastomeric curable materials and multifunctional elastomeric curable materials. and the total concentration of monofunctional elastomeric curable material is from about 30% to about 50% (e.g., from about 40% to about 45%), or from about 50% to about 70% (e.g., about 55%) by weight. % to about 60% by weight), the total concentration of the multifunctional elastomeric curable material ranges from about 10% to about 20% by weight, and the one or more blends It further includes additional monofunctional curable materials at a total concentration in the range of about 30% by weight.

According to some of any of the embodiments described herein, the one or more building compounds include at least one elastomeric monofunctional curable material, at least one elastomeric multifunctional curable material, and at least one elastomeric multifunctional curable material. Contains a type of additional monofunctional curable material.

According to some of any of the embodiments described herein, the total concentration of curable monofunctional materials ranges from 10% to 30% by weight of the total weight of the one or more building compounds. be.

According to some of any of the embodiments described herein, the total concentration of elastomeric monofunctional curable material ranges from 50% to 70% by weight of the total weight of the one or more building compounds. It is.

According to some of any of the embodiments described herein, the total concentration of elastomeric multifunctional curable material ranges from 10% to 20% by weight of the total weight of the one or more building compounds. It is.

According to some of any of the embodiments described herein, the total concentration of curable monofunctional materials ranges from 10% to 30% by weight of the total weight of the one or more building compounds. , the total concentration of elastomeric monofunctional curable materials ranges from 50% to 70% by weight of the total weight of the one or more building compounds; It ranges from 10% to 20% by weight of the total weight of the modeling compound.

According to some of any of the embodiments described herein, the total concentration of curable monofunctional materials ranges from 20% to 30% by weight of the total weight of the one or more building compounds. be.

According to some of any of the embodiments described herein, the total concentration of elastomeric monofunctional curable material ranges from 30% to 50% by weight of the total weight of the one or more building compounds. It is.

According to some of any of the embodiments described herein, the total concentration of elastomeric multifunctional curable material ranges from 10% to 30% by weight of the total weight of the one or more building compounds. It is.

According to some of any of the embodiments described herein, the total concentration of curable monofunctional materials ranges from 20% to 30% by weight of the total weight of the one or more building compounds. , the total concentration of elastomeric monofunctional curable materials is in the range of 30% to 50% by weight of the total weight of the one or more building compounds, and the total concentration of elastomeric multifunctional curable materials is It ranges from 10% to 30% by weight of the total weight of the modeling compound.

In the exemplary build material formulations described herein, the concentration of each component may be expressed as a concentration when one build material formulation is used, or as a concentration when more than one build material formulation is used. is given as its total concentration when used.

In some embodiments, an elastomeric build material formulation (or two or more build material formulations) as described herein, when cured, produces at least 4000 N/m, or at least 4500 N/m m, or at least 5000 N/m. Tear resistance is determined according to ASTM D624.

In some embodiments, an elastomeric build material formulation (or two or more build material formulations) as described herein, when cured, contains the same cured material without the silica particles. Characterized by a tear resistance that is at least 500 N/m, or at least 700 N/m, or at least 800 N/m higher than the tear resistance of the building material formulation.

In some embodiments, an elastomeric build material formulation (or two or more build material formulations) as described herein is characterized by a tensile strength of at least 2 MPa when cured. .

In some embodiments, an elastomeric build material formulation (or two or more build material formulations) as described herein comprises a cured build material and includes two O-rings. The object comprising the tube connecting the rings is such that it is characterized by tear resistance under constant stretching for at least one hour or at least one day.

According to some of the embodiments described herein, the elastomeric curable material is the same as described herein for the elastomeric curable material in each embodiment and any combination thereof. selected from monofunctional elastomer curable monomers, monofunctional elastomer curable oligomers, multifunctional elastomer curable monomers, multifunctional elastomer curable oligomers, and any combination thereof, as described in .

In some embodiments, the elastomeric curable material is represented by formulas I, I ^* , II, and III, as described herein in each embodiment and in any combination thereof. Contains one or more materials selected from materials.

According to some of any of the embodiments described herein, the elastomeric curable material and the silica particles are in the same formulation.

According to some of any of the embodiments described herein, the elastomeric curable formulation system further comprises at least one additional curable material.

According to some of the embodiments described herein, the additional curable material is present for the additional curable material in each embodiment and any combination thereof. Selected from monofunctional curable monomers, monofunctional curable oligomers, multifunctional curable monomers, multifunctional curable oligomers, and any combination thereof, as described herein.

According to some of any of the embodiments described herein, the elastomeric curable material, the silica particles, and the additional curable material are in the same formulation.

According to some of any of the embodiments described herein, the elastomeric curable material is a UV curable elastomeric material.

According to some of any of the embodiments described herein, the elastomeric curable material is an acrylic elastomer.

object:
Embodiments of the invention provide three-dimensional objects that include at least a portion of a soft material that resembles soft body tissue.

Embodiments of the invention provide three-dimensional objects that resemble body structures as defined herein, including soft body tissues or organs.

Embodiments of the invention provide a three-dimensional object that includes at least a portion of a soft material that has at least the visual and mechanical properties of soft body tissue, or a body organ, system or structure containing it.

According to some of the embodiments described herein, the object comprises a material having a Shore A hardness of less than 10 or a Shore OO hardness of less than 40, as described herein. Included in at least some of them.

According to part of any of the embodiments described herein, an object described herein may be any of the objects described herein for each of the embodiments and any combinations thereof. can be obtained by additive manufacturing methods such as

When an object is made from a single soft build material formulation, as described herein, when it is cured (solidified) it It has mechanical properties as described.

In some embodiments, the object is made from two or more building material formulations, and in some of these embodiments, at least a portion of the object is digitally constructed as described herein. made from materials. In some embodiments, the object includes a core-sheath structure as described herein in any of the respective embodiments, and has properties according to the selected material and structure.

The object according to this embodiment is such that at least part or portion thereof is made from a soft material. The object can be such that several parts or parts thereof are made of a soft material, or the whole is made of a soft material. The soft material can be the same or different in different parts or parts, and for each part, part or all of an object made from a soft material, the soft material can be the same or different within the part, part or object. Or it can be different. When different soft materials are used, they can differ in their chemical composition and/or mechanical properties, as explained further below.

As part of any of the embodiments described herein, objects include visual characteristics (e.g., shape, sensation, etc.) of body structures (e.g., body systems, tissues, and/or organs as defined herein). , color, appearance) and mechanical properties (for example, Shore hardness).

In some of any of the embodiments described herein, the object has at least the shape and hardness of a body structure, including body soft tissue, as described herein.

In some of these embodiments, the body structure (e.g., body tissue or organ or system) includes, for example, muscle tissue, meat, skin tissue, adipose tissue, brain tissue, bone marrow tissue, liver as described herein. tissue, cartilage tissue, tumor tissue, smooth tissue, and any other soft tissue.

In some of the embodiments described herein, the object as described herein is part of a medical device, such as a medical device used for training or educational purposes. or form it. Exemplary such devices are provided in FIGS. 10, 11A and 11B.

According to part of any of the embodiments described herein, the object preferably has visual properties (e.g. shape and color) and mechanical properties (e.g. hardness). Such objects resemble, for example, a heart, bones, brain, blood vessels, muscles, skin or flesh, and any combination thereof.

Exemplary such objects are provided in FIGS. 9D and 17, for example.

In some of any of the embodiments described herein, the object is devoid of biological material, as described herein.

The term "about" as used herein refers to ±10% or ±5%.

The terms "comprises," "including," "having," and their cognates mean "including but not limited to." .

The term "consisting of" means "including and limited to."

The expression "consisting essentially of" is used only when the additional ingredients, steps and/or moieties do not materially alter the essential novel characteristics of the claimed composition, method or structure. , means that the composition, method or structure may include additional components, steps and/or parts.

As used herein, the singular forms (“a,” “an,” and “the”) include plural references unless the context clearly dictates otherwise. For example, the term "a compound" or the term "at least one compound" can encompass multiple compounds, including mixtures thereof.

Throughout this application, various aspects of the invention may be presented in a range format. It is to be understood that the description in range format is merely for convenience and brevity and is not to be construed as an inflexible limitation on the scope of the invention. Accordingly, range statements should be construed to include all possible subranges specifically disclosed as well as the individual numerical values included within that range. For example, the description of a range such as 1 to 6 refers to specifically disclosed subranges (e.g., 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc.), and , shall be considered to have the individual numerical values within that range (eg, 1, 2, 3, 4, 5, and 6). This applies regardless of the scope.

Whenever a numerical range is expressed herein, it is meant to include any recited numbers (fractional or integer) that fall within the indicated range. The expressions “ranging between” the first indicated number and the second indicated number, and “from” the first indicated number “to” the second indicated number; The expression "range ranging from/to" is used interchangeably and is meant to include the first indicated number, the second indicated number, and all fractions and integers therebetween.

Throughout this specification, the term "(meth)acrylic" includes acrylic and methacrylic compounds.

Throughout this specification, the expression "linking moiety" or "linking group" describes a group that connects two or more moieties or groups in a compound. The linking moiety is generally derived from a di- or trifunctional compound and can be viewed as a two or three radical moiety, where the two or three radicals are connected via their two or three atoms, respectively. Connected to two or three other parts.

Exemplary linking moieties, when defined as a hydrocarbon moiety or chain, and/or linking group, optionally interrupted by one or more heteroatoms, as defined herein: containing any of the chemical groups listed in

When a chemical group is referred to herein as a "terminal group," it is interrupted as a substituent, and the substituent is connected to another group by one of its atoms.

Throughout this specification, the term "hydrocarbon" collectively describes chemical groups composed primarily of carbon and hydrogen atoms. Hydrocarbons can consist of alkyls, alkenes, alkynes, aryls, and/or cycloalkyls, each of which may be substituted or unsubstituted and interrupted by one or more heteroatoms. The number of carbon atoms can range from 2 to 20, preferably lower, for example from 1 to 10, or from 1 to 6, or from 1 to 4. The hydrocarbon can be a linking group or a terminal group.

Bisphenol A is an example of a hydrocarbon composed of two aryl groups and one alkyl group.

The term "amine" as used herein describes both the groups -NR'R" and -NR'-, where R' and R" are each independently hydrogen, alkyl, cycloalkyl, or aryl, as these terms are defined herein below.

Thus, amine groups include primary amines (where R' and R'' are both hydrogen), secondary amines (where R' is hydrogen and R'' is alkyl, cycloalkyl, or aryl). ), or a tertiary amine where R' and R'' are each independently alkyl, cycloalkyl or aryl.

Alternatively, R' and R'' are each independently hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy , aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, carbonyl, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, It can be an N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine.

The term "amine" is used herein to represent a -NR'R" group, as defined herein below, when the amine is a terminal group and also when the amine is a terminal group. Used herein to represent a -NR'- group when part of a linking group or moiety.

The term "alkyl" describes saturated aliphatic hydrocarbons including straight and branched chain groups. Preferably, the alkyl group has 1 to 3 or 1 to 20 carbon atoms. Whenever a numerical range is mentioned herein, such as "1 to 20," it means that the group (in this case the alkyl group) has 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. up to 20 carbon atoms. Alkyl groups can be substituted or unsubstituted. A substituted alkyl can have one or more substituents, each substituent independently including, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, Amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate , O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine.

An alkyl group is a terminal group (as this term is defined herein above) attached to a single adjacent atom, or two or more moieties through at least two carbons in the chain. (as that term is defined herein above). When alkyl is the linking group, it is also referred to herein as an "alkylene" or "alkylene chain."

As used herein, C(1-4) alkyl substituted by a hydrophilic group, as defined herein, is included under the expression "hydrophilic group" herein.

Alkenes and alkynes as used herein are alkyls, as defined herein, containing one or more double or triple bonds, respectively.

The term "cycloalkyl" group describes an all-carbon monocyclic group or a fused-ring (i.e., ring sharing a pair of adjacent carbon atoms) group in which one or more of the rings does not have a fully conjugated pi-electron system. do. Examples include, but are not limited to, cyclohexane, adamatine, norbornyl, isobornyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. A substituted cycloalkyl can have one or more substituents, each substituent independently being, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic , amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thio It can be a carbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A cycloalkyl group includes a terminal group (as this term is defined herein above) attached to a single adjacent atom, or two or more via at least two carbons in the chain. It can be a linking group (as that term is defined herein above) that connects the components.

Cycloalkyl of 1 to 6 carbon atoms, as defined herein, substituted by two or more hydrophilic groups are included herein under the expression "hydrophilic group".

The term "heteroalicyclic" group describes a monocyclic or fused ring group having one or more atoms in the ring(s), such as, for example, nitrogen, oxygen, and sulfur. The ring can also have one or more double bonds. However, the ring does not have a fully conjugated pi-electron system. Representative examples are piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino and analogs thereof.

Heteroalicyclics can be substituted or unsubstituted. A substituted heteroalicyclic ring can have one or more substituents, each substituent being independently, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, Heteroalicyclic, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, It can be N-thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A heteroalicyclic group is a terminal group (as this term is defined herein above) attached to a single adjacent atom, or two or more via at least two carbons in the chain. can be a linking group (as that term is defined herein above) that connects the components of.

Heteroalicyclic groups containing one or more electron-donating atoms, such as nitrogen or oxygen, and having a numerical ratio of carbon atoms to heteroatoms of 5:1 or lower, are defined herein as "hydrophilic groups". Included below.

The term "aryl" group describes an all-carbon monocyclic or fused polycyclic (ie, rings sharing adjacent pairs of carbon atoms) group having a fully conjugated pi-electron system. Aryl groups can be substituted or unsubstituted. A substituted aryl can have one or more substituents, each substituent independently being, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic , amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thio It can be a carbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. An aryl group is a terminal group (as this term is defined herein above) attached to a single adjacent atom, or two or more moieties through at least two carbons in the chain. (as that term is defined herein above).

The term "heteroaryl" group refers to a monocyclic group having one or more atoms in the ring(s), such as, for example, nitrogen, oxygen and sulfur, and also having a fully conjugated pi-electron system or Fused ring (ie, rings sharing adjacent pairs of carbon atoms) groups are described. Non-limiting examples of heteroaryl groups include pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, isoquinoline and purine. A heteroaryl group can be substituted or unsubstituted. A substituted heteroaryl can have one or more substituents, each substituent being independently, e.g., hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroaryl. Ring, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N- It can be a thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, or hydrazine. A heteroaryl group includes a terminal group (as this term is defined herein above) attached to a single adjacent atom, or two or more terminal groups attached through at least two carbons in the chain. It can be a linking group (as that term is defined herein above) that connects the components. Representative examples are pyridine, pyrrole, oxazole, indole, purine and the like.

The terms "halide" and "halo" describe fluorine, chlorine, bromine, or iodine.

The term "haloalkyl" describes an alkyl group as defined above further substituted by one or more halides.

The term "sulfate" refers to an -O-S(=O) ₂ -OR' terminal group or an -O-S(=O) ₂ -O- linking group, as these terms are defined herein above. ) in which R' is as defined herein above.

The term "thiosulfate" refers to the -O-S(=S)(=O)-OR' terminal group or the -O-S(=S)(=O)-O- linking group (as these terms are used herein). (as defined herein above) in which R' is as defined herein above.

The term "sulfite" refers to an -O-S(=O)-O-R' terminal group or an -O-S(=O)-O- linking group, as these terms are defined herein above. where R' is as defined herein above.

The term "thiosulfite" refers to an -O-S(=S)-O-R' terminal group or an -O-S(=S)-O- linking group (as these terms are defined herein above). where R' is as defined herein above.

The term "sulfinate" refers to the -S(=O)-OR' terminal group or the -S(=O)-O- linking group, as these terms are defined herein above, in the formula , R' are as defined herein above).

The term "sulfoxide" or "sulfinyl" refers to an -S(=O)R' terminal group or a -S(=O)- linking group (as these terms are defined herein above) (formula (in which R' is as defined herein above).

The term "sulfonate" refers to a -S(=O) ₂ -R' terminal group or a -S(=O) ₂ - linking group, as these terms are defined herein above, in the formula , R' are as defined herein above).

The term "S-sulfonamide" refers to a -S(=O) ₂ -NR'R" terminal group or an -S(=O) ₂ -NR'- linking group (as these terms are defined herein above). (where R' and R'' are as defined herein above).

The term "N-sulfonamide" refers to an R'S(=O) ₂ -NR" terminal group or an -S(=O) ₂ -NR'- linking group (as these terms are defined herein above). (where R' and R'' are as defined herein above).

The term "disulfide" refers to an -S-SR' terminal group or an S-S- linking group (as these terms are defined herein above), where R' (as defined in ).

The term "phosphonate" refers to a -P(=O)(OR')(OR") terminal group or -P(=O)(OR') with R' and R" as defined herein. (O)-represents a linking group (these expressions are as defined herein above).

The term "thiophosphonate" refers to a -P(=S)(OR')(OR") terminal group or a -P(=S)(OR") with R' and R" as defined herein. ')(O)-represents a linking group (these expressions are as defined herein above).

The term "phosphinyl" refers to a -PR'R' terminal group or -PR'- linking group with R' and R' as defined herein above (these expressions are defined herein above). ).

The term "phosphine oxide" refers to a -P(=O)(R')(R") terminal group or a -P(=O)(R') with R' and R" as defined herein. ) - represents a linking group (these expressions are as defined herein above).

The term "phosphine sulfide" refers to a -P(=S)(R')(R") terminal group or a -P(=S)(R') with R' and R" as defined herein. ) - represents a linking group (these expressions are as defined herein above).

The term "phosphite" refers to an -O-PR'(=O)(OR") terminal group or -O-PH(=O)(O-PH) with R' and R" as defined herein. ) - represents a linking group (these expressions are as defined herein above).

The term "carbonyl" or the term "carbonate" as used herein refers to a -C(=O)-R' terminal group with R' as defined herein or a -C( =O)-represents a linking group (these expressions are as defined herein above).

The term "thiocarbonyl" as used herein refers to a -C(=S)-R' terminal group with R' as defined herein or -C(=S)- Represents a linking group (as these expressions are defined herein above).

The term "oxo" as used herein refers to a (=O) group in which an oxygen atom is connected by a double bond to an atom (e.g., a carbon atom) at the indicated position. Ru.

The term "thiooxo" as used herein refers to a (=S) group in which a sulfur atom is connected to an atom (e.g., a carbon atom) at the indicated position by a double bond. Ru.

The term "oxime" describes a =N-OH terminal group or a =N-O- linking group (as these terms are defined herein above).

The term "hydroxyl" describes the group -OH.

The term "alkoxy" describes both -O-alkyl and -O-cycloalkyl groups as defined herein.

The term "aryloxy" describes both -O-aryl and -O-heteroaryl groups as defined herein.

The term "thiohydroxy" describes the group -SH.

The term "thioalkoxy" describes both -S-alkyl and -S-cycloalkyl groups as defined herein.

The term "thioaryloxy" describes both -S-aryl and -S-heteroaryl groups as defined herein.

"Hydroxyalkyl", also referred to herein as "alcohol", describes an alkyl, as defined herein, substituted with a hydroxy group.

The term "cyano" describes the group -C≡N.

The term "isocyanate" describes the group -N=C=O.

The term "isothiocyanate" describes the group -N=C=S.

The term "nitro" describes the group _-NO2 .

The term "acylhalide" describes the group -(C=O)R"", where R"" is halide as defined herein above.

The term "azo" or "diazo" refers to a -N=NR' terminal group or -N=N- linking group, as these terms are defined herein above, where R' is (as defined herein above).

The term "peroxo" refers to an -O-OR' terminal group or an -O-O- linking group, as these terms are defined herein above, where R' is (as defined above).

The term "carboxylate" as used herein includes C-carboxylate and O-carboxylate.

The term "C-carboxylate" refers to a -C(=O)-OR' terminal group or a -C(=O)-O- linking group, as these terms are defined herein above. (wherein R' is as defined herein above).

The term "O-carboxylate" refers to an -OC(=O)R' terminal group or an -OC(=O)- linking group (as these terms are defined herein above) in the formula , R' are as defined herein above).

Carboxylates can be linear or cyclic. When cyclic, R' and the carbon atom are linked together to form a ring with the C-carboxylate, and this group is also designated as a lactone. Alternatively, R' and O are linked together to form a ring with O-carboxylate. Cyclic carboxylates can function as linking groups, for example, when an atom in the ring formed is linked to another group.

The term "thiocarboxylate" as used herein includes C-thiocarboxylate and O-thiocarboxylate.

The term "C-thiocarboxylate" refers to a -C(=S)OR' terminal group or a -C(=S)-O- linking group, as these terms are defined herein above. (wherein R' is as defined herein above).

The term "O-thiocarboxylate" refers to an -OC(=S)R' terminal group or an -OC(=S)- linking group (as these terms are defined herein above) (formula (in which R' is as defined herein above).

Thiocarboxylates can be linear or cyclic. When cyclic, R' and the carbon atom are joined together to form a ring with C-thiocarboxylate, and this group is also designated as a thiolactone. Alternatively, R' and O are linked together to form a ring with O-thiocarboxylate. A cyclic thiocarboxylate can function as a linking group, for example, when an atom in the ring formed is linked to another group.

The term "carbamate" as used herein includes N-carbamates and O-carbamates.

The term "N-carbamate" refers to an R"OC(=O)-NR'- terminal group or an -OC(=O)-NR'- linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

The term "O-carbamate" refers to an -OC(=O)-NR'R" terminal group or an -OC(=O)-NR'- linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

Carbamates can be linear or cyclic. When cyclic, R' and the carbon atom are linked together to form a ring with the O-carbamate. Alternatively, R' and O are linked together to form a ring with the N-carbamate. A cyclic carbamate can function as a linking group, for example, when an atom in the ring formed is linked to another group.

The term "carbamate" as used herein includes N-carbamates and O-carbamates.

The term "thiocarbamate" as used herein includes N-thiocarbamates and O-thiocarbamates.

The term "O-thiocarbamate" refers to an -OC(=S)-NR'R" terminal group or an -OC(=S)-NR'- linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

The term "N-thiocarbamate" refers to an R"OC(=S)NR'-terminal group or an -OC(=S)NR'-linking group, as these terms are defined herein above. ) in which R' and R'' are as defined herein above.

The thiocarbamate can be linear or cyclic, as described herein for carbamates.

The term "dithiocarbamate" as used herein includes S-dithiocarbamates and O-thiodithiocarbamates.

The term "S-dithiocarbamate" refers to a -SC(=S)-NR'R" terminal group or a -SC(=S)NR'- linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

The term "N-dithiocarbamate" refers to an R"SC(=S)NR'-terminal group or a -SC(=S)NR'-linking group, as these terms are defined herein above. ) in which R' and R'' are as defined herein above.

The term "urea" (also referred to as "ureido") refers to the -NR'C(=O)-NR"R"' terminal group or the -NR'C(=O)-NR"- linking group ( These terms are as defined herein above) (wherein R' and R'' are as defined herein above and R'' is for R' and R'' (as defined herein).

The term "thiourea" (also referred to as "thiouraid") refers to the -NR'C(=S)-NR"R"' terminal group or the -NR'-C(=S)-NR"- linkage. The group (as these terms are defined herein above) is described, where R', R" and R"' are as defined herein above.

The term "amide" as used herein includes C-amide and N-amide.

The term "C-amide" refers to a -C(=O)-NR'R" terminal group or a -C(=O)-NR'- linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

The term "N-amide" refers to an R'C(=O)-NR"-terminal group or an R'C(=O)-N-linking group, as these terms are defined herein above. (where R' and R'' are as defined herein above).

Amides can be linear or cyclic. When cyclic, R' and the carbon atom are joined together to form a ring with C-amide, and this group is also designated as a lactam. A cyclic amide can function as a linking group, for example, when an atom in the ring formed is linked to another group.

The term "guanyl" refers to an R'R"NC(=N)-terminal group or a -R'NC(=N)-linking group (as these terms are defined herein above) (formula where R' and R'' are as defined herein above.

The term "guanidine" refers to the -R'NC(=N)-NR"R"' terminal group or the -R'NC(=N)-NR"- linking group (as these terms are defined herein above). (where R', R" and R"' are as defined herein above).

The term "hydrazine" refers to an -NR'-NR"R"' terminal group or -NR'-NR"- linking group, as these terms are defined herein above, in which R ', R'' and R'' are as defined herein above.

As used herein, the term "hydrazide" means -C(=O)-NR'-NR"R, where R', R" and R"' are as defined herein. "'terminal group or -C(=O)-NR'-NR"-represents a linking group (as these expressions are defined herein above).

As used herein, the term "thiohydrazide" means -C(=S)-NR'-NR" where R', R" and R"' are as defined herein. R"' represents a terminal group or a -C(=S)-NR'-NR"-linking group (as these expressions are defined herein above).

As used herein, the term "alkylene glycol" refers to an -O-[(CR'R") _z -O] _y -R"' terminal group or an -O-[(CR'R") _z - O] _y -represents a linking group, where R', R" and R"' are as defined herein, and z is an integer from 1 to 10, preferably from 2 to is an integer of 6, more preferably an integer of 2 or 3, and y is an integer of 1 or more. Preferably, R' and R'' are both hydrogen. When z is 2 and y is 1, the group is ethylene glycol. When z is 3 and y is 1, the group is propylene glycol. When y is 2-4, the alkylene glycol is referred to herein as oligo(alkylene glycol).

When y is greater than 4, the alkylene glycol is designated herein as poly(alkylene glycol). In some embodiments of the invention, the poly(alkylene glycol) group or poly(alkylene glycol) moiety is such that z is from 1 to 200, preferably from 1 to 100, more preferably from 10 to It can have from 1 to 20 repeating alkylene glycol units, such as 50.

The term "silanol" describes the group -Si(OH)R'R' or -Si(OH) _2R ' or -Si(OH) ₃ , where R' and R' are defined herein. It is as it is said.

The term "silyl" describes the group -SiR'R"R"', where R', R" and R"' are as defined herein.

As used herein, the term "urethane" or "urethane moiety" or "urethane group" refers to the R _X -O-C(=O)-NR'R" terminal group or the _-R (=O)NR' describes a linking group, R' and R'' are as defined herein, and R _X is alkyl, cycloalkyl, aryl, alkylene glycol or any combination thereof. be. Preferably R' and R'' are both hydrogen.

The term "polyurethane" or "oligourethane" includes at least one urethane group as described herein in a repeating backbone unit, or a urethane bond -O-C(=O) in a repeating backbone unit. A portion containing at least one NR'- is described.

It will be appreciated that certain features of the invention, which are, for clarity, described in the context of separate embodiments, can also be provided in combination in a single embodiment. Conversely, various features of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or other described embodiments of the invention. You can also. Certain features described in the context of various embodiments should not be considered essential features of those embodiments unless that embodiment is inoperable without those elements. .

Throughout this specification, whenever the expression "wt%" or "weight percent" or "%wt." , is meant as a weight percent of the total weight of the respective uncured formulation.

Each of the various embodiments and aspects of the invention as delineated herein above and as claimed in the claims section below find experimental support in the Examples below. .

Reference is now made to the examples below which, together with the above description, illustrate the invention in a non-limiting manner.

Example 1
Formulation Design The inventor has determined that a Shore hardness value of less than 10, preferably less than 1, or 0 on the Shore A scale, and/or a Shore hardness value of less than 50, preferably less than 40, or less than 30 on the Shore OO scale. When used in additive manufacturing methods such as 3D inkjet printing, the curable material has a range of viscosity, mechanical properties and/or appearance properties of the resulting cured material (see Figure 7). We have explored possible building material formulations.

As described above, such soft construction materials are particularly suitable for providing 3D objects, at least in part of which have properties that mimic soft body tissue.

As further described above, to date, the lowest Shore hardness value obtainable for 3D inkjet printed cured materials is about 27 on the Shore hardness A scale.

The Shore hardness of currently practiced 3D inkjet printed curable building materials is primarily due to the exclusive inclusion of curable materials in the building formulations that provide them.

Materials exhibiting low hardness, such as those shown above, are generally gel-like materials (e.g. materials with the mechanical properties of a gel), which means that in addition to curable materials, formulations also contain non-curable materials. obtained from. Such gel-like materials are currently most often used in additive manufacturing as support materials, which are intended to be removed at the end of the process and not form part of the final object.

Herein and in the industry, the term "gel" describes a material often referred to as a semi-solid material, which is generally a three-dimensional solid made from chemically or physically linked fibrous structures. a network and a liquid phase engaged within the network. Gels are generally characterized by a solid consistency (e.g. non-fluid), a relatively low tensile strength, a relatively low shear modulus, e.g. less than 100 kPa, and a loss shear modulus for storage shear modulus of less than 1. (tan δ G''/G').

The gel-like material according to this embodiment is generally a soft material, which can be a gel or a solid, and which has the mechanical and flow properties of a gel.

However, such gel-like materials exhibit low tensile strength and low tensile resistance and therefore easily fail under stress, properties that are less desirable for additive manufacturing in general and 3D inkjet printing in particular, and even when exposed to water. , easy to damage when using. Additionally, gel-like materials generally impose print reliability problems such as smearing and sticking, and are also characterized by low dimensional stability due to leakage, sweating, or drying. Gel-like materials are further limited by their ability to swell other components and thus may form incompatible or at least unstable bodies when used in multi-material (eg digital materials) technology.

A solution to the limitations associated with utilizing formulations that, when cured, provide gel-like materials is the use of reinforcing materials that provide improved strength and/or provide desired stiffness and/or durability. encapsulation of a gel-like material in the material shown, such a solution can give the cured material overall properties, especially hardness, that exceed the target properties.

Liquid materials can also be added to the formulation to balance the overall properties, but such materials may adversely affect the performance of the resulting object, e.g. cause a "bleeding" effect, and/or Adversely affects the mechanical properties of the object (generally reduces crosslink density). Therefore, the amount of liquid material should be selected to give the desired effect with minimal adverse effects.

Therefore, the inventors have determined that the desired hardness value, preferably other properties for efficient additive manufacturing of objects, such as tensile strength, tensile resistance, stability (long shelf life), dimensional stability, Build material formulations or formulation systems provided in combination with other curable materials (e.g., when used in the formation of digital materials in 3D inkjet printing) Considered sufficient combinations of curable and non-curable materials to be included.

The tested formulations, and the curable materials or objects made from them, were tested when used on their own and in combination with other curable formulations, as formulation systems in a multi-material (digital material (DM)) approach. Characterized when used. The tested formulations are further for use in printing objects comprising at least in part a material (having mechanical and appearance properties) that mimics the soft tissues of the body, as described herein. were characterized for their suitability to provide a cured material suitable for use.

Example 2
Formulations Table 1 below provides exemplary formulations according to the present embodiments, which have a Shore Scale A hardness of 0 (determined by no reading when measured using a Shore A durometer according to ASTM D2240) shows.

The expression "monofunctional acrylate type I" used in Table 1 refers to monofunctional hydrophilic or hydrophilic amphiphilic acrylates, in particular acrylate groups as polymerizable groups and one or more heteroatoms (e.g. O, N or both). ) or heteroatom-containing groups (e.g., carboxylates, amides, alkylene glycols, and combinations thereof) that confer hydrophilic or amphiphilic properties. includes. See also equation A1. where R ₁ is C(=O)-O-Ra, and Ra is a hydrophilic or amphiphilic moiety free of hydrophobic groups or moieties as described herein. Exemplary materials include alkoxy-terminated poly(ethylene glycol) acrylates (e.g., sold as AM130); urethane acrylates (e.g., sold as Genomer®, e.g., Genomer 1122); acryloylmorpholine, and others described herein. each of the curable materials.

The expression "monofunctional acrylate type II" refers to an acrylate group as the polymerizable group and at least one hydrophobic moiety or group (e.g. a hydrocarbon of at least 6 carbon atoms in length as defined herein). ) of one or more monomers, oligomers or polymers, preferably monomeric hydrophobic or hydrophobic amphiphilic curable materials. See also equation A2. where R ₁ is C(=O)-O-Ra, and Ra is or includes a hydrophobic moiety or group. Exemplary such materials include compounds of formula A as described herein having nonyl, phenyl, isodecyl, and/or lauryl groups as Ra groups, optionally in combination with alkylene glycol groups, such as SR395 ; including those sold by Sartomer as SR504D, SR335, SR7095, etc.

As used in the Examples section of this specification, the expression "non-curable polymeric material" refers to polymerizable acrylate groups that contribute to polymerization when exposed to conditions that initiate acrylate polymerization, as described herein. or lacking any other polymerizable groups (e.g., lacking groups that polymerize upon exposure to radiation at wavelengths that induce acrylate polymerization or photopolymerizable groups). . Preferably, the non-curable polymeric materials have varying Tg values when cured and are available under the trade name "Pluronic®" in any order and number of blocks in any MW. PEG and PPG, also known as block copolymers. Preferably, the non-curable polymeric material comprises one or more block copolymers of PEG and PPG, such as PEG-PPG-PEG and PPG-PEG-PPG, which contains up to 10% by weight of PEG, and herein with a PEG/PPG ratio as described and a MW of at least 500, preferably at least 900, more preferably at least 2000 Daltons, and/or when cured as described herein. , less than 20°C, preferably less than 0°C, more preferably less than -20°C. Preferably, these materials are characterized by low solubility (eg less than 20% or less than 10% or less) or insolubility in water.

The expression "multifunctional acrylate" includes one or more monomeric, oligomeric or polymeric curable materials comprising two or more polymerizable acrylate groups. Such materials are also referred to herein as crosslinkers. Exemplary such materials include, but are not limited to, urethane diacrylates such as those sold as Ebecryl 230; e.g. trimethylolpropane triacrylate, optionally ethoxylated (e.g. Photomer 4072, Photomer 4158, Photomer 4149, Photomer 4006, Miramer M360, SR499), glyceryl triacrylate, pentaerythritol tetraacrylate, optionally ethoxylated (e.g. sold as Photomer 4172), hexanediol diacrylate, PEGDA, and also epoxy diacrylates such as those sold as Photomer 3005, Photomer 3015, Photomer 3016, Photomer 3316. Preferably, the multifunctional acrylate has a Tg of less than 20°C or less than 0°C when cured.

The term "polysiloxane" encompasses non-curable organic and inorganic materials containing a polysiloxane backbone, including, by way of non-limiting example, PDMS and its derivatives and block copolymers containing the same.

The terms "photoinitiator" and "inhibitor" are as defined herein.

All formulations given in Table 1 contain one or more photoinitiators in amounts ranging from 1 to 5% (eg 3%) by weight. Exemplary photoinitiators include those of the Irgacure® family, such as I819, I184, and combinations thereof.

All formulations given in Table 1 contain one or more inhibitors (free radical polymerization inhibitors) in amounts ranging from 0.01 to 1% by weight (eg 0.1% by weight). Exemplary inhibitors include tris(N-nitroso-N-phenylhydroxylamine) aluminum salt (NPAL) and the Genorad® family of inhibitors, such as G18.

Some of the formulations given in Table 1 further include additional non-reactive ingredients (additives) as described herein.

In an exemplary formulation (BM219), a UV curable surfactant (BYK UV-3500-polyether modified acrylic functional polydimethylsiloxane) is used.

Additional exemplary formulations were made that included polyfunctional acrylates other than urethane diacrylates in amounts of 1 to 3% by weight, and/or polysiloxane compounds in amounts of 5 to 10% by weight, all of which It had a Shore A hardness of 0 as defined herein.

Example 3
Characterization The following preliminary tests were performed to characterize the cured materials obtained from the formulations tested during the design process.

Shore A hardness was determined according to ASTM D2240 with a Shore A durometer.

Shore OO hardness was determined according to ASTM D2240 using a Shore OO durometer.

The compressive modulus was measured using a Stratasys J750™ 3D printer for cylindrical uncoated objects with a radius of 20 mm and a height of 15 mm, which were themselves printed from the tested formulations. The decision was made regarding The test used a Lloyd instrument system, 100N load cell operated with the following parameters: direction = compression; preload/stress = 0.5N; preload/stress speed = 50mm/min; speed = 50mm/min; limit = 8mm. It was carried out as follows. Stress versus strain data was extracted from the obtained data and the slope between strain values of 0.001 and 0.01 was calculated. Satisfactory values in these measurements are in the range of 0.02 to 0.1 MPa. The data obtained in these tests are also referred to herein as "compressive stress at 40% strain."

The same Lloyd system was used for adhesion testing and operated with the following parameters: direction = tension; deceleration = 2 mm/min; acceleration = 5 mm/min; force drop = -5 N; hold time = 1 s. Specimens in which the tested formulation was used as a coating are measured and results are reported as the maximum load required to pull the platen out of the coated specimen.

Tear resistance (TR) was determined according to ASTM D624 for the specimens described therein with a thickness of 2 mm. Values are reported here as load (N) at maximum load for 2 mm thick specimens. A satisfactory value for these measurements is at least 0.3N. For some formulations, the time to failure measured in this test is also reported; a satisfactory value is at least 9 seconds. The reported values were converted to N/m tear resistance values as stated, where they were divided by 0.002. For example, the value of 0.3N reported here is equal to 150N/m.

Stability is determined for uncoated objects (printed from formulations tested themselves) or coated objects (printed with a 0.8 mm coating of elastomeric curable materials (e.g. from the Agilus family, e.g. Agilus 30). All were printed using a Stratasys J750TM 3D printer, with a cubic shape of 25 mm x 25 mm x 25 mm, and once printed, the resulting objects were weighed and the objects were stored at 50 °C for 7 days. , reweighed using an analytical scale. Weight changes relative to the initial weight after printing are given in weight %.

Dimensional stability was determined on coated elliptical objects of 60 x 24 x 18 mm coated with a 0.6 mm layer of elastomeric curable material (e.g. Agilus family, e.g. Agilus 30) and kept at 50 °C for several days. or store it at room temperature for one month and observe the distortion in the object after storage. An acceptable result would be no distortion.

Post-print tack is quantitatively determined for printed objects shaped as cubes by applying tissue paper to the object and giving a rating on a scale of 0-3 as follows: 3 if it cannot be removed from the object and 0 if there are no fibers stuck to the object once the tissue paper is removed.

Printing of the 3D objects was performed using a Stratasys J750 3D printer.

All formulations have a Shore A hardness of 0, and some formulations have values of 0 to 30 when tested for their Shore AOO hardness.

Table 2A below summarizes data obtained by characterizing exemplary formulations according to the present embodiments given in Table 1 using the experimental methods described above.

Adhesion tests as described above were carried out by printing cubic samples (15 mm x 15 mm x 15 mm) made from a building compound such as that sold as Vero, coated with a 0.6 mm thick layer of the tested compound. It was carried out by The resulting samples were tested while still (wet) and after drying with a cloth (dry). The following data were obtained: BM151 (wet) - load at maximum load = 1.3N; BM151 (dry) - load at maximum load = 7.3N.

In different sets of experiments, the formulations given in Table 1 as BM205.4 and BM219 were characterized as follows.

Shore OO hardness is measured on uncoated objects (printed from the formulation itself tested) or coated objects (printed with a 0.6 mm coating of elastomeric curable material, such as Agilus 30); All were printed using a Stratasys J750TM 3D printer according to ASTM D2240 using a Shore OO durometer for 6 mm height samples.

The compressive modulus was measured using a cylindrical Agilus 30 coated object made from the tested formulation, with a radius of 20 mm and a height of 15 mm, printed using a Stratasys J750 3D printer. It was decided about. The test was carried out using a Lloyd equipment system, 100N load cell, with the following parameters: direction = compression; preload/stress = 0.5N; preload/stress speed = 50mm/min; speed = 50mm/min; limit = 90N It was operated with. Stress vs. strain data was extracted from the obtained data and the slope between strain values of 0.001 and 0.01 was calculated.

Load to failure for cubic Agilus-coated objects made from the tested formulations, printed using a Stratasys J750 (trade name) 3D printer and having dimensions of 50 x 50 x 50 mm. It has been determined. The test was carried out using a Lloyd equipment system, 100N load cell, operated with the following parameters: direction = compression; preload/stress = 0.5N; preload/stress speed = 50mm/min; speed = 50mm/min; The load to failure was determined to be the maximum load that the sample could sustain before ultimate failure.

Stability was measured using a Stratasys J750TM 3D printer on Agilus-coated cubic objects made from the formulation tested itself and having dimensions of 50 mm x 50 mm x 50 mm, once printed. The resulting body was weighed, stored at 50° C. for 3 days, and reweighed using an analytical scale. Weight changes relative to the initial weight after printing are given in weight %.

The data obtained are given in Table 2B below.

Printability, adhesion to the roller, and amount of material in the roller bath after leveling were observed quantitatively, showing good printability for most of the formulations tested, and for some formulations, the amount of material in the roller bath after leveling was For the other formulations, no stickiness to the roller was observed and the roller bath was clean.

Stability was also measured in terms of color change over time. For some formulations, some change in color was observed after 4 weeks at room temperature, and for exemplary formulations such as BM205.4 and BM219, no change in color was observed during this period. . The data obtained showed that the properties of the curable materials obtained from the tested formulations were determined by the weight ratio of curable to non-curable materials, the type of curable and non-curable materials, and the characteristics of the multifunctional curable materials. It was suggested that it is influenced by type and amount. Accordingly, advantageous formulations include materials with a low Tg as described and defined herein, which preferably have a low Tg as defined herein. less than 50% by weight of a non-curable material, at least 3% by weight, preferably at least 5% by weight (e.g. 5-10% by weight) of a multifunctional curable material with a low Tg, as defined herein. %). Some properties are also influenced by the type and amount of inhibitor and/or the addition of surfactants.

Example 4
Suitability in Multi-Material Additive Manufacturing As noted above, the present formulations have utility in multi-material additive manufacturing, particularly where improved strength and tear resistance while maintaining low hardness is required. Some of the formulations tested were used to form printed bodies that were coated or covered with elastomeric materials (eg, the Agilus family, eg Agilus 30), as they can be coated. Therefore, the swelling of Agilus 30™ in the non-curable material included in the exemplary formulations provided herein is consistent with the chemical conditions of the non-curable material in which the elastomeric material exhibits minimal swelling. Tested for the purpose of specifying.

The swelling test is carried out by printing swelling test specimens made from cured elastomeric material (e.g. Agilus family, e.g. Agilus 30) with dimensions of 20 x 20 x 1 mm and measuring each using an analytical scale. This was done by recording the weight of the specimen. Each specimen was placed in a 20 ml glass vial and 15 ml of the tested non-reactive material (test material) was added to it. A sample without additional material was used as a control. The vials were stored at 40-50°C and after 3-4 days the samples were dried using a cloth and analyzed using an analytical scale. Tables 3 and 4 below give the weight changes obtained.

As can be seen from Table 3, high molecular weight materials comprising or consisting of PPG blocks at high contents provide improved performance when used with Agilus 30.

As can be seen in Table 4, high swelling is observed in the exemplary support material formulations and in the presence of other additives commonly added to build materials (e.g. PEG400; propanediol); , improved dimensional stability is observed.

Example 5
3D Inkjet Printing One mode of application of the formulations of this embodiment is in the 3D inkjet printing of objects for modeling comprising at least a portion of a soft material (eg 0 Shore A hardness).

The inventor utilized formulations according to this embodiment in a multi-material 3D inkjet printing mode with elastomeric materials.

As shown in Examples 2 and 3 above, we have demonstrated dimensional stability, reduced or eliminated tackiness, and leakage of non-reactive materials into other materials used in multi-material mode. or have identified formulations that provide buildable objects that have reduced or eliminated migration (eg, swelling).

In order to ensure reliable and proper 3D inkjet printing of objects for construction, it is preferable to use materials that have at least one of the following characteristics:
(i) Stability over time reflected in a long shelf life of the printed body without shape distortion, layer separation, material leakage, and wrinkle/cracking development.
These properties are verified using the following exemplary tests:
Delamination test on sandwich specimens: 20 x 20 x 5 mm specimens made from a soft material formulation as described herein and covered with a 1 mm layer of Agilus 30Clear™ were printed and incubated at 50°C. It will be maintained for 3 days. Thereafter, peeling of the coating layer is observed. Acceptable results are minimal or no flaking.
Delamination test on elliptical specimens: 60 x 24 x 18 mm specimens of ellipticals made from a soft material formulation as described herein and coated with a 0.6 mm layer of Agilus 30 were printed and ℃ for 3 days or at room temperature for 1 month. The dimensions of the specimen are then tested. An acceptable result is minimal or no distortion.
Delamination test on box-shaped specimens: 40 x 30 x 20 mm box-shaped objects coated with Agilus 30 layer are printed as above and kept at 50° C. for 3 days. The integrity, weight, and dimensions of the box are then measured. An acceptable result is a deviation of less than 3% from the parameters measured immediately after printing.
(ii) reflected, for example, by tear resistance (controlled, slow and preferably nullified crack propagation when the printed object is subjected to moderate stress), peel resistance, and cutting and/or sewing resistance; Resistance to Applied Force Tear resistance is verified using ASTM as described in Example 3.
Peel resistance is verified using the T-peel test (ASTM D1876), which was performed to measure maximum yield load and crack propagation load. Acceptable results are greater than 15N for maximum yield load and greater than 13N for crack propagation load.
The sewing/stitching test verifies the resistance to sewing through the printed matrix as depicted in FIG.
(iii) Print reliability as reflected by print quality and accuracy. These characteristics are verified using the following exemplary tests:
Accurate printing of 100x40z5mm plates; and adequate printing quality of simple object geometries such as cubes, spheres and cylinders, and complex geometries such as body organs, e.g. heart models.
(iv) a color that reflects the desired stimulus, e.g. the appearance of a tissue mimic (e.g. of human flesh) and is visually tested; this characteristic is achieved by using coloring systems already known in the industry; (e.g. colored with Vero Yellow and Vero Magenta coloring systems).

Several 3D inkjet printing modes utilizing soft material formulations according to the present embodiments and elastomeric materials as described herein have been practiced and found to meet the above conditions, as follows. .
(a) an object made from a soft material formulation as described herein covered by a thin (e.g. 0.5-1 mm) sheath layer of an elastomeric material as described herein; Provides multiple material core-sheath printing mode. The left and center objects in FIG. 8 give images of elliptical objects coated with a 0.7 mm thick layer of Agilus 30.
Tear resistance data for similar objects is given in Example 3 above.
Objects printed according to this sheath-core mode exhibited dimensional stability, printability, mechanical properties, and printing reliability that met the conditions set forth above.
(b) a composite structure made from a soft material formulation as described herein and reinforced by a scaffold made from an elastomeric material in addition to being covered by a sheath of an elastomeric material as described above; Multi-material scaffolding mode that gives you a multi-material scaffolding mode. The scaffolding material can be 19-26% by weight of the total weight of the multi-material formulation system, as exemplified herein for BM19 (see Table 1). The BM19 formulation reinforced with 19% Agilus 30 as scaffold has a modulus of 100 kPa and improved tear resistance.

FIG. 9A is a schematic diagram of a printing scheme for forming regions containing interlaced build material, and FIG. 9B shows an exemplary thin plate printed according to the scheme shown in FIG. 9A, and FIG. 3 is an image comprising a scaffold composite structure of BM61 with 19% Agilus30 scaffold.

The object on the right side of FIG. 8 provides an elliptical structure made from a composite scaffold of a soft material formulation and an elastomeric formulation as described herein and covered by an elastomeric material.

Figures 9C and 9D show a heart model made from BM19 formulation (see Table 1) reinforced by Agilus30 scaffold structure (19% 0.5 mm beam) (Figure 9C), and a view of its interior (Figure 9D). give.

Objects printed according to this scaffolding reinforcement mode exhibited dimensional stability, printability, mechanical properties, and printing reliability that met the conditions indicated above.

These data are described herein while obtaining the desired softness (0 Shore A hardness), but usable strength (e.g. tear resistance), desired stability over time, and desired printability. It has been successfully used to print 3D objects made from soft material formulations.

As an example, FIG. 10 gives an image of an object printed using BM61 with 19% Agilus30 scaffold and 0.6 mm Agilus30 coating. It withstands sutures/sewing through it.

Figures 11A-B provide cardiac mimetics printed using BM61 with 19% Agilus30 scaffold and 0.6 mm Agilus30 coating and tested on a medical device.

When printed without coating, good printing reliability, dimensional and color stability over time, resistance to force, along with the necessary soft properties were achieved with the MB205.4 and MB219 formulations.

Example 6
Optimization of Printing Parameters: Using soft material formulations as described herein while reducing the amount of reinforcing material (e.g. elastomeric material) and improving print reliability issues such as stickiness to the rollers of AM systems. Further studies were conducted to optimize the printing parameters for use.

In this example, a Jarvik heart model, such as the model shown in FIG. 12, was printed. All heart models were constructed using the BM151 and BM151 described above in an interlaced voxel fashion such that for each layer, approximately Printed by jetting the Agilus 30 formulation. Experiments were conducted with X=10, X=11, X=14, and X=19.

An elastomeric building compound was dispensed in a DM operating mode with the building material formulation to form a three-dimensional DM structure in which the elements of the building material formulation were within the support material matrix. The three-dimensional DM structure acts as a temporarily removable support structure for the fabricated object (in this example a heart model) and is referred to herein as a support grid. Three different sizes for the build material formulation elements in the support structure were tested in this example: about 0.2 mm diameter, about 0.4 mm diameter, and about 1 mm diameter. The support grids obtained for these sizes are referred to herein as support grid A, support grid B, and support grid C. The shape of these building material formulation elements was generally cubic. For support grid A, the ratio of the amount of building material formulation to the amount of elastomeric building compound is approximately 12%, and for support grid B, the ratio of the amount of building material formulation to the amount of elastomeric building compound is approximately 12%. The ratio between the amounts of the building material formulation and the elastomer building formulation was about 25% for support grid C.

It has been found by the inventor that the rotational speed of the roller is influenced by the quality of the printed material. For soft materials, but not specifically limited to, for materials obtained using the exemplary formulation described in Example 1 above, We have found it preferable to use a roller rotation speed of RPM of . The effect of the rotation speed of the roller on the smoothness of the outer surface is shown in Figures 13A-B, where Figure 13A is an image of a heart model printed in a mode where the roller is rotated at a speed of 600 RPM, and Figure 13B is an image of a heart model printed in a mode where the roller is rotated at a speed of 600 RPM. , an image of a heart model printed in a mode where the rollers are rotated at a speed of 412 RPM. The heart model shown in FIG. 13B has a substantially smoother outer surface than the heart model shown in FIG. 13A. The region with defects is marked by the dotted circle in FIG. 13A.

The inventors have discovered that good quality of the printed body is given by printing in matte mode, in which the outermost surface of the object is coated with one or more layers of support material (support material) that are subsequently removed. It was found that there are no contour gaps that leave the voxels covered by the body grid B) blank between the boundaries of the support grid and the boundaries of the model. The effect of contour gap on the smoothness of the outer surface is shown in FIG. Two heart models are shown. The heart model on the left was printed in a mode in which contour gaps were used, and the heart model on the right was printed in a mode in which contour gaps were not used. The heart model shown on the right side of FIG. 14 has a substantially smoother outer surface than the heart model shown on the left side of FIG. The region with the defect is marked by a dotted circle in the image of the heart model on the left side of FIG.

An elastomeric building compound (eg Agilus 30) was included both to reduce the adhesion of each layer and to stiffen the object. The inventors have found that fiber reinforcement provides higher tear resistance than non-fiber reinforcement, and that directional fiber reinforcement patterns provide higher tear resistance than isotropic fiber reinforcement patterns. Without wishing to be bound by any particular theory, it is believed that the tearing force applied by the rollers is oblique to the plane of the layer as shown schematically in FIG. 15. A freshly dispensed layer of a material combination designated TM and a roller rolling over the surface of the layer to reinforce the newly dispensed layer are shown. The force exerted by the roller includes a component T resulting from the relative translational movement between the layer and the roller, and a component R resulting from the rotational movement of the roller. The combination of components T and R results in an effective force F that is oblique to the plane engaged by the top surface of the layer (the XY plane perpendicular to the XZ plane shown in FIG. 15).

Figures 16A-F show several experimentally tested reinforcement patterns in the XZ plane. Vertical reinforcement pattern (parallel to thickness direction Z, Fig. 16A), horizontal reinforcement pattern (perpendicular to thickness direction Z, Fig. 16B), positive diagonal pattern (positive inclination with respect to the plane engaged by the layer, Fig. 16C), a negative diagonal pattern (negative slope with respect to the plane engaged by the layer, FIG. 16D), and two isotropic patterns (an indented pattern (FIG. 16E) and a gyroid pattern (FIG. 16F)). shown.

Experiments showed that the vertical and negative diagonal reinforcement patterns exhibited higher tear resistance than other reinforcement patterns. The highest tear resistance was obtained with X=14, a negative reinforcement pattern with a slope of about −45°, Agilus 30 fibers of about 0.5 mm diameter, and an outermost Agilus 30 coating of about 0.4 to about 0.7 mm. Ta. Figure 17 is an image of four heart models printed using these parameters.

Although the invention has been described in terms of specific embodiments thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art. Accordingly, the present invention includes all such alternatives, modifications, and variations that come within the spirit and broad scope of the appended claims.

All publications, patents, and patent applications mentioned in this specification are herein incorporated by reference in their entirety to the same extent as if each individual publication, patent, and patent application was specifically and individually cited by reference. It is intended to be used in Furthermore, citation or identification in this application is not to be construed as an admission that such references are available as prior art to the present invention. To the extent that section headings are used, they should not necessarily be construed as limiting.

Claims (58)

A method for the additive manufacturing of objects representing soft body tissues, the method comprising: dispensing by inkjet technology at least one building material formulation to sequentially form a plurality of layers in a pattern of construction corresponding to the shape of the object. and for at least a portion of the layer, the discharge is of a photopolymerizable building material formulation having a Shore A hardness of less than 1 or a Shore OO hardness of less than 40 when cured. and the method includes heating the photopolymerizable building material formulation, prior to the dispensing, to a temperature at which the photopolymerizable building material formulation exhibits a viscosity of less than or equal to X centipoise. , where X is 27 to 33. said discharge is of at least two building material formulations, at least one of said building material formulations having a Shore A hardness of less than 1 or a Shore OO hardness of less than 40 when cured; 2. The method of claim 1, wherein the building material formulation is an elastomeric curable formulation, and at least one of the building material formulations is an elastomeric curable formulation comprising at least one elastomeric curable material. 3. The method of claim 2, wherein the elastomeric curable formulation further comprises silica particles. Claim: said dispensing comprises forming a voxel element comprising said building material formulation and an elastomeric curable formulation having a Shore A hardness of less than 1 or a Shore OO hardness of less than 40 when cured. The method according to item 2 or 3. 4. The interlaced locations occupied by the elastomeric curable formulation constitute between X% and Y% of the area of the layer, where X is from 9 to 11 and Y is from 27 to 33. The method according to any one of 2 to 4. The interlaced locations occupied by the elastomeric curable formulation constitute between X% and Y% of the area of the layer, where X is from 13.5 to 16.5 and Y is from 22.5 to 27.5. The method according to any of claims 2 to 4. A method according to any of claims 2 to 6, wherein the voxel elements comprising the elastomeric curable formulation form a three-dimensional fiber pattern in the object. The fiber thickness according to claim 7, which indicates the characteristics of the fiber pattern, is from Xmm to Ymm, where X is from 0.36 to 0.44, and Y is from 0.54 to 0.66. Method. 9. A method according to claim 7 or 8, wherein the fiber pattern is perpendicular to at least two or three planes of the layer. 9. A method according to claim 7 or 8, wherein the fiber pattern is oblique to at least two or three planes of the layer. The method further comprises reinforcing each of at least two or three of the layers using a roller, wherein the diagonal fiber pattern resists tear forces applied by the roller on the layer. 11. The method of claim 10, wherein the two are parallel with an offset of less than 10[deg.]. A method according to claim 10 or 11, wherein the fiber pattern forms an angle between X° and Y° with respect to the plane, where X is between 27 and 33 and Y is between 54 and 66. 13. The method of any of claims 2 to 12, further comprising forming a sheath covering an object from the elastomeric curable formulation. The thickness of the sheath measured perpendicular to the outermost surface of the sheath is between X mm and Y mm, where X is between 0.36 and 0.44 and Y is between 0.9 and 1.1. 14. The method according to claim 13. 15. The method further comprises forming a sheath covering an object from the elastomeric curable formulation and removing the sheath covering the object after completion of the additive manufacturing of the object. Method described in Crab. the build material formulation having a Shore A hardness of less than 1 or a Shore OO hardness of less than 40 when cured comprises a curable material and a non-curable polymeric material, an amount of the non-curable polymeric material; is in the range of 10 to 49% or 10 to 30% by weight of the total weight of the formulation. 17. The method of claim 16, wherein the amount of non-curable polymeric material ranges from 20 to 40% by weight. 18. A method according to claim 16 or 17, wherein the non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons and a Tg of less than 0°C or less than -10°C or less than -20°C. A method according to any of claims 16 to 18, wherein the non-curable polymeric material comprises polypropylene glycol. A method according to any of claims 16 to 19, wherein the non-curable polymeric material is a block copolymer comprising at least one polypropylene glycol block. 16. The non-curable polymeric material is a block copolymer comprising at least one polypropylene glycol block and at least one polyethylene glycol block, and the total amount of the polyethylene glycol in the block copolymer is 10% by weight or less. 20. The method according to any one of 20 to 20. 22. The method of claim 21, wherein the ratio of polypropylene glycol blocks to polyethylene glycol blocks in the block copolymer is at least 2:1. Any of claims 16 to 22, wherein the non-curable polymeric material comprises polypropylene glycol and/or a block copolymer comprising at least one polypropylene glycol block, each polypropylene glycol block having a molecular weight of at least 2000 Daltons. Method described in Crab. Any of claims 16 to 23, wherein the ratio of the amount of curable material to the amount of non-curable polymeric material ranges from 4:1 to 1.1:1 or from 3:1 to 2:1. Method described. A method according to any of claims 16 to 24, wherein the amount of curable material ranges from 55 to 70% by weight. A method according to any of claims 16 to 25, wherein the curable material comprises at least one monofunctional curable material and at least one multifunctional curable material. 27. The method of claim 26, wherein the amount of monofunctional curable material ranges from 50 to 89% by weight of the total weight of the formulation. 28. A method according to claim 26 or 27, wherein the amount of multifunctional curable material ranges from 1 to 10% by weight of the total weight of the formulation. The formulation comprises a monofunctional curable material in an amount of 50-89% by weight, a non-curable polymeric material in an amount of 10-49% by weight, and a multifunctional curable material in an amount of 1-10% by weight. The method according to any one of claims 16 to 28. (i) said non-curable polymeric material has a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons, and/or (ii) said non-curable polymeric material has a molecular weight of less than 0°C or less than -10°C or - has a Tg of less than 20°C, and/or (iii) at least 80% by weight of the total amount of said monofunctional curable material and said multifunctional curable material, when cured, is less than 0°C or less than -10°C; or comprising a curable material with a Tg of less than -20°C.
30. The method of claim 29. A method according to any of claims 26 to 30, wherein the amount of monofunctional curable material ranges from 50 to 60% or from 55 to 60% by weight. 32. A method according to any of claims 26 to 31, wherein the amount of multifunctional curable material ranges from 3 to 10% or from 5 to 10% by weight. 33. A method according to any of claims 23 to 32, wherein the monofunctional curable material, when cured, has a Tg of less than -10°C or less than -20°C. A method according to any of claims 26 to 33, wherein the monofunctional curable material comprises a hydrophobic monofunctional curable material. 35. A method according to any of claims 26 to 34, wherein the monofunctional curable material comprises an amphiphilic monofunctional curable material. 36. The method of claim 35, wherein the amphiphilic monofunctional curable material includes a hydrophobic moiety. 37. The method of any of claims 26 to 36, wherein the monofunctional curable material comprises an amphiphilic monofunctional curable material comprising a hydrophobic moiety and a hydrophobic monofunctional curable material. 38. The method of claim 37, wherein the weight ratio of the amphiphilic monofunctional curable material to the hydrophobic monofunctional curable material ranges from 1.5:1 to 1.1:1. 39. A method according to any of claims 26 to 38, wherein the multifunctional curable material, when cured, has a Tg of less than -10°C or less than -20°C. A method according to any of claims 26 to 38, wherein the multifunctional curable material is a difunctional curable material. A method according to any of claims 26 to 40, wherein the monofunctional curable material is a UV curable material. 42. A method according to any of claims 26 to 41, wherein the monofunctional curable material is a monofunctional acrylate. 43. A method according to any of claims 26 to 42, wherein the multifunctional curable material is a UV curable material. 44. A method according to any of claims 26 to 43, wherein the multifunctional curable material is a multifunctional acrylate. 45. A method according to any of claims 41 to 44, wherein the formulation further comprises a photoinitiator. 46. The method of claim 45, wherein the amount of photoinitiator ranges from 1 to 3% by weight of the total weight of the formulation. When cured, the building material formulation having a Shore A hardness of less than 1 or a Shore OO hardness of less than 40 comprises a monofunctional amphiphilic acrylate containing a hydrophobic moiety in an amount of 25 to 35% by weight. , a monofunctional hydrophobic acrylate in an amount of 25 to 30% by weight, a polyfunctional acrylate in an amount of 5 to 10% by weight, and an amount of 30 to 35% by weight of a molecular weight of at least 1000 or at least 1500 or at least 2000 Daltons and 0 47. The method of any of claims 26 to 46, comprising a non-curable polymeric material having a Tg of less than 0.degree. C. or less than -10.degree. C. or less than -20.degree. 48. The non-curable polymeric material comprises polypropylene glycol and/or a block copolymer comprising at least one polypropylene glycol block, each of the at least one polypropylene glycol block having a molecular weight of at least 2000 Daltons. Method described. 49. The method according to claim 47 or 48, wherein the polyfunctional acrylate is urethane diacrylate. A method according to any of claims 47 to 49, wherein the monofunctional amphiphilic acrylate comprises a hydrocarbon chain of at least 6 carbon atoms and at least 2 alkylene glycol groups. 51. A method according to any of claims 47 to 50, wherein the monofunctional hydrophobic acrylate comprises a hydrocarbon chain of at least 8 carbon atoms. 52. A method according to any of claims 1 to 51, wherein the formulation having the Shore hardness, when cured, is further characterized by a tear resistance of at least 100 N/m. 53. A method according to any of claims 1 to 52, wherein the formulation having the Shore hardness when cured is further characterized by a compressive modulus of at least 0.01 MPa. 54. A method according to any preceding claim, wherein at least the building material formulation having a Shore A hardness of less than 1 when cured is a synthetic material. 55. A method according to any preceding claim, wherein when cured, at least the building material formulation having a Shore A hardness of less than 1 contains less than 10% water by weight. 56. A method according to any preceding claim, wherein at least the building material formulation having the Shore hardness when cured further comprises a pigment which imparts a red color to the formulation when cured. 57. A method according to any of claims 5 to 56, wherein the elastomeric curable formulation further comprises a pigment that imparts a yellowish white opaque color to the formulation when cured. 58. A method according to claim 56 or 57, wherein the amount of pigment ranges from 0.01 to 5% by weight of the total weight of the formulation.

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